1. Technical Field
The present invention is related to polycyclic polymers and methods for their use as photoresists in the manufacture of integrated circuits. More specifically, the invention is directed to photoresist compositions comprising a polycyclic polymer and a cationic photoinitiator. The polycyclic polymer contains recurring acid labile groups that are pendant from the polymer backbone. The acid labile groups can be selectively cleaved to form recurring polar groups along the backbone of the polymer. The polymers are transparent to short wave lengths of imaging radiation and exhibit resistance to reactive ion etching.
2. Background
Integrated circuits (IC""s) are paramount in the manufacture of an array of electronic devices. They are fabricated from the sequential formation of alternating and interconnecting bands of conductive, semiconductive and nonconductive layers on an appropriate substrate (e.g., silicon wafer) that are selectively patterned to form circuits and interconnections to produce specific electrical functions. The patterning of IC""s is carried out according to various lithography techniques known in the art. Photolithography employing ultraviolet (UV) light and increasingly deep UV light or other radiation is a fundamental and important technology utilized in the production of IC devices. A photosensitive polymer film (photoresist) is applied over the wafer surface and dried. A photomask containing the desired patterning information is then placed in close proximity to the photoresist film. The photoresist is irradiated through the overlying photomask by one of several types of imaging radiation including UV light, e-beam electrons, x-rays, or ion beam. Upon exposure to radiation, the photoresist undergoes a chemical change with concomitant changes in solubility. After irradiation, the wafer is soaked in a solution that develops (i.e., selectively removes either the exposed or unexposed regions) the patterned images in the photosensitive polymer film. Depending on the type of polymer used, or the polarity of the developing solvent, either the exposed or nonexposed areas of film are removed in the developing process to expose the underlying substrate, after which the patterned exposed or unwanted substrate material is removed or changed by an etching process leaving the desired pattern in a functional layer of the wafer. Etching is accomplished by plasma etching, sputter etching, and reactive ion etching (RIE). The remaining photoresist material functions as a protective barrier against the etching process. Removal of the remaining photoresist material gives the patterned circuit.
In the manufacture of patterned IC devices, the processes of etching different layers on the wafer are among the most crucial steps involved. One method is to immerse the substrate and patterned resist in a chemical bath which attacks the exposed substrate surfaces while leaving the resist itself intact. This xe2x80x9cwetxe2x80x9d chemical process suffers from the difficulty of achieving well defined edges on the etched surfaces. This is due to chemical undercutting of the resist material and the formation of an isotropic image. In other words, conventional chemical processes do not provide the selectivity of direction (anisotropy) considered necessary to achieve optimum dimensional specifications consistent with current processing requirements. In addition, the wet processes suffer because of the undesirable environmental and safety ramifications.
Various xe2x80x9cdryxe2x80x9d processes have been developed to overcome the drawbacks of the wet chemical process. Such dry processes generally involve passing a gas through a chamber and ionizing the gas by applying a potential across two electrodes in the presence of the gas. The plasma containing the ionic species generated by the potential is used to etch a substrate placed in the chamber. The ionic species generated in the plasma are directed to the exposed substrate where they interact with the surface material forming volatile products that are removed from the surface. Typical examples of dry etching are plasma etching, sputter etching and reactive ion etching.
Reactive ion etching provides well defined vertical sidewall profiles in the substrate as well as substrate to substrate etching uniformity. Because of these advantages, the reactive ion etching technique has become the standard in IC manufacture.
Two types of photoresists are used in the industry, negative and positive photoresists. Negative resists, upon exposure to imaging radiation, polymerize, crosslink, or change solubility characteristics such that the exposed regions are insoluble to the developer. Unexposed areas remain soluble and are washed away. Positive resists function in the opposite way, becoming soluble in the developer solution after exposure to imaging radiation.
One type of positive photoresist material is based upon phenol-formaldehyde novolac polymers. A particular example is the commercially utilized Shipley AZ1350 material which comprises an m-cresol formaldehyde novolak polymer composition and a diazoketone (2-diazo-1-napthol-5-sulphonic acid ester). When exposed to imaging radiation, the diazoketone is converted to a carboxylic acid, which in turn converts the phenolic polymer to one that is readily soluble in weak aqueous base developing agent.
U.S. Pat. No. 4,491,628 to Ito et al. discloses positive and negative photoresist compositions with acid generating photoinitiators and polymers with acid labile pendant groups. Because each acid generated causes deprotection of multiple acid labile groups this approach is known as chemical amplification which serves to increase the quantum yield of the overall photochemical process. The disclosed polymers include vinylic polymers such as polystyrenes, polyvinylbenzoates, and polyacrylates that are substituted with recurrent pendant groups that undergo acidolysis to produce products that differ in solubility than their precursors. The preferred acid labile pendant groups include t-butyl esters of carboxylic acids and t-butyl carbonates of phenols. The photoresist can be made positive or negative depending on the nature of the developing solution employed.
Trends in the electronics industry continually require IC""s that are faster and consume less power. To meet this specification the IC must be made smaller. Conducting pathways (i.e., lines) must be made thinner and placed closer together. The significant reduction in the size of the transistors and the lines produced yields a concomitant increase in the efficiency of the IC, e.g., greater storage and processing of information on a computer chip. To achieve thinner line widths, higher photoimaging resolution is necessary. Higher resolutions are possible with shorter wave lengths of the exposure source employed to irradiate the photoresist material. However, the prior art photoresists such as the phenol-formaldehyde novolac polymers and the substituted styrenic polymers contain aromatic groups that inherently become increasingly absorptive as the wave length of light falls below about 300 nm, (ACS Symposium Series 537, Polymers for Microelectronics, Resists and Dielectrics, 203rd National Meeting of the American Chemical Society, Apr. 5-10, 1992, p.2-24; Polymers for Electronic and Photonic Applications, Edited by C. P. Wong, Academic Press, p. 67-118). Shorter wave length sources are typically less bright than traditional sources which necessitate a chemical amplification approach using photoacids. The opacity of these aromatic polymers to short wave length light is a drawback in that the photoacids below the polymer surface are not uniformly exposed to the light source and, consequently, the polymer is not developable. To overcome the transparency deficiencies of these polymers, the aromatic content of photoresist polymers must be reduced. If deep UV transparency is desired (i.e., for 248 nm and particularly 193 nm wave length exposure), the polymer should contain a minimum of aromatic character.
U.S. Pat. No. 5,372,912 concerns a photoresist composition containing an acrylate based copolymer, a phenolic type binder, and a photosensitive acid generator. The acrylate based copolymer is polymerized from acrylic acid, alkyl acrylate or methacrylate, and a monomer having an acid labile pendant group. While this composition is sufficiently transparent to UV radiation at a wave length of about 240 nm, the use of aromatic type binders limits the use of shorter wave length radiation sources. As is common in the polymer art, the enhancement of one property is usually accomplished at the expense of another. When employing acrylate based polymers, the gain in transparency to shorter wave length UV is achieved at the expense of sacrificing the resist""s resistance to the reactive ion etch process.
In many instances, the improvement in transparency to short wave length imaging radiation results in the erosion of the resist material during the subsequent dry etching process. Because photoresist materials are generally organic in nature and substrates utilized in the manufacture of IC""s are typically inorganic, the photoresist material has an inherently higher etch rate than the substrate material when employing the RIE technique. This necessitates the need for the photoresist material to be much thicker than the underlying substrate. Otherwise, the photoresist material will erode away before the underlying substrate could be fully etched. It follows that lower etch rate resist materials can be employed in thinner layers over the substrate to be etched. Thinner layers of resist material allow for higher resolution which, ultimately, allows for narrower conductive lines and smaller transistors.
J. V. Crivello et al. (Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, 376-381) describe a polymer blend comprising 20 weight % of a free radically polymerized homopolymer of a norbornene monomer bearing acid labile groups and 80 weight % of a homopolymer of 4-hydroxy-xcex1-methylstyrene containing acid labile groups for use in electron-beam photoresists. As discussed supra, the increased absorbity (especially in high concentrations) of aromatic groups renders these compositions opaque and unusable for short wave length imaging radiation below 200 nm.
The disclosed compositions are suitable only for electron-beam photoresists and can not be utilized for deep UV imaging (particularly not for 193 nm resists).
Crivello et al. investigated blend compositions because they observed the oxygen plasma etch rate to be unacceptably-high for free radically polymerized homopolymers of norbornene monomers bearing acid labile groups.
Accordingly, there is a need for a photoresist composition which is compatible with the general chemical amplification scheme and provides transparency to short wave length imaging radiation while being sufficiently resistant to a reactive ion etching processing environment.
It is a general object of the invention to provide a photoresist composition comprising a polycyclic polymer backbone having pendant acid labile groups and a photoinitiator.
It is another object of the invention to provide polycyclic polymers that have recurrent pendant acid labile groups that can be cleaved to form polar groups.
It is still another object of the invention to provide polymer compositions that are transparent to short wave length imaging radiation.
It is a further object of the invention to provide polymer compositions that are resistant to dry etching processes.
It is a still further object of the invention to provide polymer compositions that are transparent to short wave length imaging radiation and are resistant to dry etching processes.
It is yet another object of the invention to provide polycyclic monomers that contain acid labile pendant groups that can be polymerized to form polymers amenable to aqueous base development.
These and other objects of the invention are accomplished by polymerizing a reaction mixture comprising an acid labile group functionalized polycycloolefinic monomer, a solvent, a single or multicomponent catalyst system each containing a Group VIII metal ion source. In the multicomponent catalyst systems of the invention the Group VIII ion source is utilized in combination with one or both of an organometal cocatalyst and a third component. The single and multicomponent catalyst systems can be utilized with an optional chain transfer agent (CTA) selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, wherein at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto. The CTA is selected from unsaturated compounds that are typically cationically non-polymerizable and, therefore, exclude styrenes, vinyl ethers, and conjugated dienes.
The polymers obtained are useful in photoresist compositions that include a radiation-sensitive acid generator.
The present invention relates to a radiation-sensitive resist composition comprising an acid-generating initiator and a polycyclic polymer containing recurring acid labile pendant groups along the polymer backbone. The polymer containing the initiator is coated as a thin film on a substrate, baked under controlled conditions, exposed to radiation in a patterned configuration, and optionally post baked under controlled conditions to further promote the deprotection. In the portions of the film that have been exposed to radiation, the recurrent acid labile pendant groups on the polymer backbone are cleaved to form polar recurring groups. The exposed areas so treated are selectively removed with an alkaline developer. Alternatively, the unexposed regions of the polymer remain nonpolar and can be selectively removed by treatment with a suitable nonpolar solvent for a negative tone development. Image reversal can easily be achieved by proper choice of developer owing to the difference in the solubility characteristics of the exposed and unexposed portions of the polymer.
The polymers of the present invention comprise polycyclic repeating units, a portion of which are substituted with acid labile groups. The instant polymers are prepared by polymerizing the polycyclic monomers of this invention. By the term xe2x80x9cpolycyclicxe2x80x9d (norbornene-type or norbornene-functional) is meant that the monomer contains at least one norbornene moiety as shown below: 
The simplest polycyclic monomer of the invention is the bicyclic monomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene. In one embodiment of the invention, the acid labile functionality is introduced into the polymer chain by polymerizing a reaction medium comprising one or more acid labile substituted polycyclic monomers set forth under Formula I below in optional combination with one or more polycyclic monomers set forth under Formulae II, III, IV, and V below in the presence of the Group VIII metal catalyst system.
In another embodiment of the invention one or more of the acid labile substituted polycyclic monomers of Formula I are copolymerized with one or more of the polycyclic monomers set forth under Formula II.
Monomers
The acid labile polycyclic monomers useful in the practice of the present invention are selected from a monomer represented by the formula below: 
wherein R1 to R4 independently represent a substituent selected from the group consisting of hydrogen linear or branched (c1 to c10) alkyl, xe2x80x94(A)nC(O)OR*, xe2x80x94(A)nxe2x80x94C(O)OR, xe2x80x94(A)nxe2x80x94OR, xe2x80x94(A)nxe2x80x94OC(O)R, xe2x80x94(A)nxe2x80x94C(O)R, xe2x80x94(A)nxe2x80x94OC(O)OR, xe2x80x94(A)nxe2x80x94OCH2C(O)OR*, xe2x80x94(A)nxe2x80x94C(O)O-Axe2x80x2xe2x80x94OCH2C(O)OR*, xe2x80x94(A)nxe2x80x94OC(O)xe2x80x94Axe2x80x2xe2x80x94C(O)OR*, xe2x80x94(A)nxe2x80x94C(R)2CH(R)(C(O)OR**), and xe2x80x94(A)nxe2x80x94C(R)2CH(C(O)OR**)2 subject to the proviso that at least one of R1 to R4 is selected from the acid labile group xe2x80x94(A)nC(O)OR*. A and Axe2x80x2 independently represent a divalent bridging or spacer radical selected from divalent hydrocarbon radicals, divalent cyclic hydrocarbon radicals, divalent oxygen containing radicals, and divalent cyclic ethers and cyclic diethers, and n is an integer of 0 or 1. When n is 0 it should be apparent that A and Axe2x80x2 represent a single covalent bond. By divalent is meant that a free valence at each terminal end of the radical are attached to two distinct groups. The divalent hydrocarbon radicals can be represented by the formula xe2x80x94(CdH2d)xe2x80x94 where d represents the number of carbon atoms in the alkylene chain and is an integer from 1 to 10. The divalent hydrocarbon radicals are preferably selected from linear and branched (C1 to C10) alkylene such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. When branched alkylene radicals are contemplated, it is to be understood that a hydrogen atom in the linear alkylene chain is replaced with a linear or branched (C1 to C5) alkyl group.
The divalent cyclic hydrocarbon radicals include substituted and unsubstituted (C3 to C8) cycloaliphatic moieties represented by the formula: 
wherein a is an integer from 2 to 7 and Rq when present represents linear and branched (C1 to C10) alkyl groups. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the following structures: 
wherein Rq is defined above. As illustrated here and throughout this specification, it is to be understood that the bond lines projecting from the cyclic structures and/or formulae represent the divalent nature of the moiety and indicate the points at which the carbocyclic atoms are bonded to the adjacent molecular moieties defined in the respective formulae. As is conventional in the art, the diagonal bond line projecting from the center of the cyclic structure indicates that the bond is optionally connected to any one of the carbocyclic atoms in the ring. It is also to be understood that the carbocyclic atom to which the bond line is connected will accommodate one less hydrogen atom to satisfy the valence requirement of carbon.
Preferred divalent cyclic ethers and diethers are represented by the structures: 
The divalent oxygen containing radicals include (C2 to C10) alkylene ethers and polyethers. By (C2 to C10) alkylene ether is meant that the total number of carbon atoms in the divalent ether moiety must at least be 2 and can not exceed 10. The divalent alkylene ethers are represented by the formula -alkylene-O-alkylene- wherein each of the alkylene groups that are bonded to the oxygen atom can be the same or different and are selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylene. The simplest divalent alkylene ether of the series is the radical xe2x80x94CH2xe2x80x94O-CH2xe2x80x94. Preferred polyether moieties include divalent radicals of the formula:
xe2x80x94(CH2(CH2)xO)yxe2x80x94
wherein x is an integer from 0 to 5 and y is an integer from 2 to 50 with the proviso that the terminal oxygen atom on the polyether spacer moiety can not be directly linked to a terminal oxygen atom on an adjacent group to form a peroxide linkage. In other words, peroxide linkages (i.e., xe2x80x94Oxe2x80x94Oxe2x80x94) are not contemplated when polyether spacers are linked to any of the terminal oxygen containing substituent groups set forth under R1 to R4 above.
In the above formulae R represents hydrogen, linear and branched (C1 to C10) alkyl, and m is an integer from 0 to 5. R* represents moieties (i.e., blocking or protecting groups) that are cleavable by photoacid initiators selected from xe2x80x94C(CH3)3, xe2x80x94Si(CH3)3, xe2x80x94CH(Rp)OCH2CH3, xe2x80x94CH(Rp)OC(CH3)3, or the following cyclic groups: 
wherein Rp represents hydrogen or a linear or branched (C1 to C5) alkyl group. The alkyl substituents include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the above structures, the single bond line projecting from the cyclic groups indicates the carbon atom ring position where the protecting group is bonded to the respective substituent. Examples of acid labile groups include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, 1-t-butoxy ethyl, dicyclopropylmethyl (Dcpm), and dimethylcyclopropylmethyl (Dmcp) groups. The alkyl substituents on the protecting groups set forth above are selected from linear and branched (C1 to C5) alkyl groups. R** independently represents R and R* as defined above. The Dcpm and Dmcp groups are respectively represented by the following structures: 
Polycyclic monomers of the above formula with a substituent selected from the group xe2x80x94(CH2)nC(R)2CH(R)(C(O)OR**) or xe2x80x94(CH2)nC(R)2CH(C(O)OR**)2 can be represented as follows: 
wherein m and xe2x80x94Axe2x80x94 are defined above.
In the above formulae m is preferably 0 or 1, more preferably m is 0. When m is 0 the preferred structures are represented below: 
wherein R1 to R4 are previously defined.
It should be apparent to those skilled in the art that any photoacid cleavable moiety is suitable in the practice of the invention so long as the polymerization reaction is not substantially inhibited by same.
The preferred acid labile group is a protected organic ester group in which the protecting or blocking group undergoes a cleavage reaction in the presence of an acid. Tertiary butyl esters of carboxylic acids are especially preferred.
The monomers described under Formula I, when polymerized into the polymer backbone, provide recurring pendant acid sensitive groups that are subsequently cleaved to confer polarity or solubility to the polymer.
The optional second monomer is represented by the structure set forth under Formula II below: 
wherein R5 to R8 independently represent a neutral or polar substituent selected consisting of hydrogen, linear or branched (c1 to c10) from the group: xe2x80x94(A)nxe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94ORxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)Rxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Rxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94Oxe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)xe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)xe2x80x94Axe2x80x2xe2x80x94ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94OC(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94Oxe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94OC(O)C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(Rxe2x80x3)2CH(Rxe2x80x3)(C(O)ORxe2x80x3), and xe2x80x94(A)nxe2x80x94C(Rxe2x80x3)2CH(C(O)ORxe2x80x3)2, or the succinic and carboxyimide moieties: 
wherein R37 is hydrogen, linear and branched (C1 to C10) alkyl, or (C6 to C15) aryl.
The moieties A and Axe2x80x2 independently represent a divalent bridging or spacer radical selected from divalent hydrocarbon radicals, divalent cyclic hydrocarbon radicals, divalent oxygen containing radicals, and divalent cyclic ethers and cyclic diethers, and n is an integer 0 or 1. When n is 0 it should be apparent that A and Axe2x80x2 represent a single covalent bond. By divalent is meant that a free valence at each terminal end of the radical are attached to two distinct groups. The divalent hydrocarbon radicals can be represented by the formula xe2x80x94(CdH2d)xe2x80x94 where d represents the number of carbon atoms in the alkylene chain and is an integer from 1 to 10. The divalent hydrocarbon radicals are preferably selected from linear and branched (C1 to C10) alkylene such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. When branched alkylene radicals are contemplated, it is to be understood that a hydrogen atom in the linear alkylene chain is replaced with a linear or branched (C1 to C5) alkyl group.
The divalent cyclic hydrocarbon radicals include substituted and unsubstituted (C3 to C8) cycloaliphatic moieties represented by the formula: 
wherein a is an integer from 2 to 7 and Rq when present represents linear and branched (C1 to C10) alkyl groups. Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the following structures: 
wherein Rq is defined above. As illustrated here and throughout this specification, it is to be understood that the bond lines projecting from the cyclic structures and/or formulae represent the divalent nature of the moiety and indicate the points at which the carbocyclic atoms are bonded to the adjacent molecular moieties defined in the respective formulae. As is conventional in the art, the diagonal bond line projecting from the center of the cyclic structure indicates that the bond is optionally connected to any one of the carbocyclic atoms in the ring. It is also to be understood that the carbocyclic atom to which the bond line is connected will accommodate one less hydrogen atom to satisfy the valence requirement of carbon.
Preferred divalent cyclic ethers and diethers are represented by the structures: 
The divalent oxygen containing radicals include (C2 to C10) alkylene ethers and polyethers. By (C2 to C10) alkylene ether is meant that the total number of carbon atoms in the divalent ether moiety must at least be 2 and can not exceed 10. The divalent alkylene ethers are represented by the formula -alkylene-O-alkylene- wherein each of the alkylene groups that are bonded to the oxygen atom can be the same or different and are selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylene. The simplest divalent alkylene ether of the series is the radical xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94. Preferred polyether moieties include divalent radicals of the formula:
xe2x80x94(CH2(CH2)xO)yxe2x80x94
wherein x is an integer from 0 to 5 and y is an integer from 2 to 50 with the proviso that the terminal oxygen atom on the polyether spacer moiety can not be directly linked to a terminal oxygen atom on an adjacent group to form a peroxide linkage. In other words, peroxide linkages (i.e., xe2x80x94Oxe2x80x94Oxe2x80x94) are not contemplated when polyether spacers are linked to any of the terminal oxygen containing substituent groups set forth under R5 to R8 above.
R5 to R8 can also independently represent hydrogen, linear and branched (C1 to C10) alkyl, so long as at least one of the remaining R5 to R8 substituents is selected from one of the neutral or polar groups represented above. In the formula above p is an integer from 0 to 5 (preferably 0 or 1, more preferably 0). Rxe2x80x3 independently represents hydrogen, linear and branched (C1 to C10) alkyl, linear and branched (C1 to C10) alkoxyalkylene, polyethers, monocyclic and polycyclic (C4 to C20) cycloaliphatic moieties, cyclic ethers, cyclic ketones, and cyclic esters (lactones). By (C1 to C10) alkoxyalkylene is meant that a terminal alkyl group is linked through an ether oxygen atom to an alkylene moiety. The radical is a hydrocarbon based ether moiety that can be generically represented as -alkylene-O-alkyl wherein the alkylene and alkyl groups independently contain 1 to 10 carbon atoms each of which can be linear or branched. The polyether radical can be represented by the formula:
xe2x80x94(CH2(CH2)xO)yxe2x80x94Ra 
wherein x is an integer from 0 to 5, y is an integer from 2 to 50 and Ra represents hydrogen or linear and branched (C1 to C10) alkyl. Preferred polyether radicals include poly(ethylene oxide) and poly(propylene oxide). Examples of monocyclic cycloaliphatic monocyclic moieties include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Examples of cycloaliphatic polycyclic moieties include, norbornyl, adamantyl, tetrahydrodicyclopentadienyl (tricyclo[5.2.1.02,6]decanyl), and the like. Examples of cyclic ethers include tetrahydrofuranyl and tetrahydropyranyl moieties. An example of a cyclic ketone is a 3-oxocyclohexanonyl moiety. An example of a cyclic ester or lactone is a mevalonic lactonyl moiety.
Insofar as the substituents described for Rxe2x80x3 in Formula II overlap with the acid labile or protecting groups described under R* in Formula I, it should be understood that Rxe2x80x3 in Formula II can not represent an ester moiety containing an acid labile group. For example, when Rxe2x80x3 is a norbornyl, adamantyl, tetrahydrodicyclopentadienyl (tricyclo[5.2.1.0 2,6]decanyl), tetrahydrofuranyl tetrahydropyranyl, 3-oxocyclohexanonyl or a mevalonic lactonyl moiety, it can not be directly attached to the oxygen atom in a ester moiety (xe2x80x94C(O)O). When any of R5 to R8 represent a succinic or carboxyimide moiety and A is present (i.e., n is 1) A can only represent a linear or branched (C1 to C10) alkylene group.
Preferred neutral or polar substituents include the alkyl esters of carboxylic acids, the spaced oxalate containing moieties (e.g., xe2x80x94(A)nxe2x80x94OC(O)xe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3), and the oxalate containing moieties (e.g., xe2x80x94(A)nxe2x80x94OC(O)C(O)ORxe2x80x3) wherein the formulae are as defined above. The ester, spaced oxalate, and oxalate containing functionalities impart exceptional hydrophilicity, promote good wetting of the developer and improve film mechanical properties without the concomitant problems associated with excessive carboxylic acid functionalities.
R5 and R8 can be taken together with the ring carbon atoms to which they are attached to form an anhydride or dicarboxyimide group as shown in the structures below: 
wherein R37 is hydrogen, (C1 to C10) alkyl, or (C6 to C15) aryl and V is an integer from 0 to 5.
The optional third monomer component is represented by the structure under Formula III below: 
wherein R9 to R12 independently represent a carboxylic or sulfonic acid substituent or salts thereof selected from the formulae xe2x80x94(CH2)nC(O)OH, xe2x80x94(CH2)nSO3H, xe2x80x94(CH2)nC(O)Oxe2x88x92X+, xe2x80x94(CH2)nSO3xe2x88x92X+ where n X represents tetraalkylammonium cations and the alkyl substituents bonded to the nitrogen atom are independently selected from linear and branched (C1 to C10) alkyl, and q is an integer from 0 to 5 (preferably 0 or 1, more preferably 0) and n is an integer from 0 to 10 (preferably 0). R9 to R12 can independently represent hydrogen, linear and branched (C1 to C10) alkyl, so long as at least one of the remaining R9 to R12 substituents is selected from one of the acids or acid salts set forth above.
The monomers containing carboxylic acid functionality contribute to the hydrophilicity of the polymer consequently aiding in the developability of the polymer in aqueous base systems at high rates.
The optional monomers under Formula IV are represented by the structure below: 
wherein R13 to R16 independently represent linear or branched (C1 to C10) alkyl and r is an integer from 0 to 5 (preferably 0 or 1, more preferably 0). Any of R13 to R16 can represent hydrogen so long as at least one of the remaining R13 to R16 substituents is selected from an alkyl group set defined above. Of the above alkyl substituents, decyl is especially preferred.
The polymerization of alkyl substituted monomers into the polymer backbone is a method to control the Tg of the polymer as disclosed in U.S. Pat. No. 5,468,819 to Goodall et al.
An economical route for the preparation of the functional or hydrocarbyl substituted polycyclic monomers of the invention relies on the Diels-Alder reaction in which cyclopentadiene (CPD) or substituted CPD is reacted with a suitably substituted dienophile at elevated temperatures to form a substituted polycyclic adduct generally shown by the following reaction scheme: 
Other polycyclic adducts can be prepared by the thermal pyrolysis of dicyclopentadiene (DCPD) in the presence of a suitable dienophile. The reaction proceeds by the initial pyrolysis of DCPD to CPD followed by the Diels-Alder addition of CPD and the dienophile to give the adducts as shown below: 
wherein Rxe2x80x2 to Rxe2x80x3xe2x80x3 independently represents the substituents defined under R1 to R16 in Formulae I, II, III, and IV above.
For example the 2-norbornene-5-carboxylic acid (bicyclo[2.2.1]hept-5-ene-2-carboxylylic acid) can be prepared by the Diels-Alder reaction of cyclopentadiene with acrylic acid in accordance with the following reaction scheme: 
The corresponding t-butyl ester of the carboxylic acid can be prepared by reacting the carboxylic acid functionality with isobutylene in the presence of triflic acid at reduced temperatures (i.e., xe2x88x9230 to xe2x88x9220xc2x0 C.) as shown in the reaction scheme below: 
Another more preferred route to the t-butyl ester of the norbornene carboxylic acid involves the Diels-Alder reaction of cyclopentadiene with t-butyl acrylate.
Another synthesis route to the acid and ester substituted monomers of the present invention is through an ortho ester substituted polycyclic monomer with subsequent hydrolysis to a carboxylic functionality or partial hydrolysis to an ester functionality. The carboxylic functionality can be esterified to the desired ester The ortho ester substituted monomers of the invention are represented by Formula V below: 
wherein R17, R18, and R19 independently represent a linear or branched (C1 to C5) alkyl group or any R17, R18, and R19 can be taken together along with the oxygen atoms to which they are attached to form a substituted or unsubstituted 5 to 10 membered cyclic or bicyclic ring containing 3 to 8 carbon atoms (excluding substituent groups), s is an integer from 0 to 5 (preferably 0), and t is an integer from 1 to 5 (preferably 1). Representative structures wherein s is 0, t is 1, and R17, R18, and R19 are taken with the oxygen atoms to which they are attached to form a cyclic or bicyclic ring are set forth below: 
wherein R17xe2x80x2, R18xe2x80x2, and R19xe2x80x2 independently represent hydrogen and linear and branched (C1 to C5) alkyl. The ortho esters of the present invention can be synthesized in accordance with the so-called Pinner synthesis (A. Pinner, Chem. Ber., 16, 1643 (1883), and via the procedure set forth by S. M. McElvain and J. T. Venerable, J. Am. Chem. Soc., 72, 1661 (1950); S. M. McElvain and C. L. Aldridge, J. Am. Chem. Soc., 75, 3987 (1953). A typical synthesis is set forth in the reaction scheme below: 
An alternative synthesis route wherein an alkyl acrylate is treated with a trialkyloxonium tetrafluoroborate salt followed by an alkali metal (sodium alcoholate) to yield the trialkoxymethyl ortho ester (H. Meerwein, P. Borner, O. Fuchs, H. J. Sasse, H. Schrodt, and J. Spille, i Chem. Ber., 89, 2060 (1956).
As discussed above the otho ester can undergo a hydrolysis reaction in the presence of dilute acid catalysts such as hydrobromic, hydroiodic, and acetic acid to yield the carboxylic acid. The carboxylic acid can in turn be esterified in the presence of an aliphatic alcohol and an acid catalyst to yield the respective ester. It should be recognized that in the case of polycyclic monomers that are di- or multi-substituted with ortho ester groups that the ortho ester moieties can be partially hydrolyzed to yield the acid and a conventional ester on the same monomer as illustrated below: 
Another and more preferred route to difunctional polycyclic monomers is through the hydrolysis and partial hydrolysis of nadic anhydride (endo-5-norbornene-2,3-dicarboxylic anhydride). Nadic anhydride can be fully hydrolyzed to the dicarboxylic acid or partially hydrolyzed to the an acid and ester functionality or diester functionality as shown below: 
wherein R17 independently represents linear and branched (C1 to C5) alkyl. Preferably R17 is methyl, ethyl, or t-butyl. In a preferred synthesis the nadic anhydride starting material is the exo-isomer. The exo-isomer is easily prepared by heating the endo-isomer at 190xc2x0 C. followed by recrystallization from an appropriate solvent (toluene). To obtain the diacid under reaction scheme 1, nadic anhydride is simply hydrolyzed in boiling water to obtain almost a quantitative yield of the diacid product. The mixed carboxylic acid-alkyl ester functionality shown in scheme 3 is obtained by heating nadic anhydride under reflux for 3 to 4 hours in the presence of the appropriate aliphatic alcohol (R17OH). Alternatively, the same product can be prepared by first reacting the nadic anhydride starting material with an aliphatic alcohol and trialkyl amine followed by treatment with dilute HCl. The diester product substituted with identical alkyl (R17) groups can be prepared from the diacid by reacting the diacid with a trialkyloxonium tetrafluoroborate, e.g., R173O[BF4], in methylene chloride at ambient temperature, in the presence of diisopropylethylamine. To obtain esters with differing R17 alkyl groups the mixed acid-ester product obtained in scheme 3 is employed as the starting material. In this embodiment the acid group is esterified as set forth in reaction scheme 2. However, a trialkyloxonium tetrafluoroborate having a differing alkyl group than the alkyl group already present in the ester functionality is employed.
It should be noted that the foregoing monomers containing the precursor functionalities can be converted to the desired functional groups before they are polymerized or the monomers can be first polymerized and then the respective polymers containing the precursor functional substituents can then be post reacted to give the desired functionality.
It is contemplated within the scope of this invention that the monomers described under Formulae I to V wherein m, p, q, r, and s is 0 the methylene bridge unit can be replaced by oxygen to give 7-oxo-norbornene derivatives.
It is also contemplated that for applications at 248 nm wave length and above R5 to R16 and R11 in Formulae II, III, and IV can be aromatic such as phenyl.
Polymers
One or more of the acid labile substituted polycyclic monomers described under Formula I are copolymerized alone or in combination with one or more of the polycyclic monomers described under Formula II, in optional combination with one or more of the polycyclic monomers described under Formulae III, IV, and V. It is also contemplated that the polycyclic monomers of Formulae I to V can be copolymerized with carbon monoxide to afford alternating copolymers of the polycyclic and carbon monoxide. Copolymers of norbornene having pendant carboxylic acid groups and carbon monoxide have been described in U.S. Pat. No. 4,960,857 the disclosure of which is hereby incorporated by reference. The monomers of Formulae I to V and carbon monoxide can be copolymerized in the presence of a palladium containing catalyst system as described in Chem. Rev. 1996, 96, 663-681. It should be readily understood by those skilled in the art that the alternating copolymers of polycyclic/carbon monoxide can exist in either the keto or spiroketal isomeric form. Accordingly, the present invention contemplates copolymers containing random repeating units derived (polymerized) from a monomer or monomers represented by Formulae I and II in optional combination with any monomer(s) represented by Formulae II to V. In addition, the present invention contemplates alternating copolymers containing repeating units derived (polymerized) from carbon monoxide and a monomer(s) represented by Formulae I to V.
Pendant carboxylic acid functionality is important from the standpoint of imparting hydrophilic character, adhesion characteristics and clean dissolution (development) properties to the polymer backbone. In some photoresist applications, however, polymers bearing excessive carboxylic acid functionalities are undesirable. Such polymers do not perform well in industry standard developers (0.26N tetramethylammonium hydroxide, TMAH). Swelling of the polymer in unexposed regions, uncontrolled thinning during application, and swelling of the polymer during exposed dissolution are inherent disadvantages associated with these highly acidic polymers. Accordingly, in situations where excessive carboxylic acid functionality is undesirable but where hydrophilicity and good wetting characteristics are essential, copolymers polymerized from the monomers of Formula I in necessary combination with the monomers of Formula II are preferred. Especially preferred are the monomers of Formula II that contain alkyl ester, alkyl carbonate spaced alkyl oxalate, and alkyl oxalate substituents such as xe2x80x94(A)nxe2x80x94C(O)ORxe2x80x3xe2x80x94, xe2x80x94(A)nxe2x80x94OC(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)xe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3 and xe2x80x94(A)nxe2x80x94OC(O)C(O)ORxe2x80x3, respectively, wherein A, Axe2x80x2, n, and Rxe2x80x3 are as defined above.
The polymers of the present invention are the key ingredient of the composition. The polymer will generally comprise about 5 to 100 mole % of the monomer (repeating unit) that contains the acid labile group component. Preferably the polymer contains about 20 to 90 mole % of the monomer that contains the acid labile group. More preferably the polymer contains about 30 to 70 mole % of the monomeric unit that contains the acid labile functionality. The remainder of polymer composition is made up of repeating units polymerized from the optional monomers set forth above under Formulae III to V. The choice and the amount of specific monomers employed in the polymer can be varied according to the properties desired. For example, by varying the amount of carboxylic acid functionality in the polymer backbone, the solubility of the polymer to various developing solvents can be adjusted as desired. Monomers containing the ester functionality can be varied to enhance the mechanical properties of the polymer and radiation sensitivity of the system. Finally, the glass transition temperature properties of the polymer can be adjusted by incorporating cyclic repeating units that contain long chain alkyl groups such as decyl.
There are several routes to polymerize cyclic olefin monomers such as norbornene and higher cyclic (polycyclic) monomers containing the norbornene moiety. These include: (1) ring-opening metathesis polymerization (ROMP); (2) ROMP followed by hydrogenation; and (3) addition polymerization. Each of the foregoing routes produces polymers with specific structures as shown in the diagram I below: 
A ROMP polymer has a different structure than that of an addition polymer. A ROMP polymer contains a repeat unit with one less cyclic unit than did the starting monomer. The repeat units are linked together in an unsaturated backbone as shown above. Because of this unsaturation the polymer preferably should subsequently be hydrogenated to confer oxidative stability to the backbone. Addition polymers on the other hand have no Cxe2x95x90C unsaturation in the polymer backbone despite being formed from the same monomer.
The monomers of this invention can be polymerized by addition polymerization and by ring-opening metathesis polymerization (ROMP) preferably with subsequent hydrogenation. The cyclic polymers of the present invention are represented by the following structures: 
wherein Rxe2x80x2 to Rxe2x80x3xe2x80x3 independently represents R1 to R19 as defined in Formulae I to V above, m is an integer from 0 to 5 and a represents the number of repeating units in the polymer backbone.
The ROMP polymers of the present invention are polymerized in the presence of a metathesis ring-opening polymerization catalyst in an appropriate solvent. Methods of polymerizing via ROMP and the subsequent hydrogenation of the ring-opened polymers so obtained are disclosed in U.S. Pat. Nos. 5,053,471 and 5,202,388 which are incorporated herein by reference.
In one ROMP embodiment the polycyclic monomers of the invention can be polymerized in the presence of a single component ruthenium or osmium metal carbene complex catalyst such as those disclosed in WO 95-US9655. The monomer to catalyst ratio employed should range from about 100:1 to about 2,000:1, with a preferred ratio of about 500:1. The reaction can be conducted in halohydrocarbon solvent such as dichloroethane, dichloromethane, chlorobenzene and the like or in a hydrocarbon solvent such as toluene. The amount of solvent employed in the reaction medium should be sufficient to achieve a solids content of about 5 to about 40 weight percent, with 6 to 25 weight percent solids to solvent being preferred. The reaction can be conducted at a temperature ranging from about 0xc2x0 C. to about 60xc2x0 C., with about 20xc2x0 C. to 50xc2x0 C. being preferred.
A preferred metal carbene catalyst is bis(tricyclohexylphosphine)benzylidene ruthenium. Surprisingly and advantageously, it has been found that this catalyst can be utilized as the initial ROMP reaction catalyst and as an efficient hydrogenation catalyst to afford an essentially saturated ROMP polymer. No additional hydrogenation catalyst need be employed. Following the initial ROMP reaction, all that is needed to effect the hydrogenation of the polymer backbone is to maintain hydrogen pressure over the reaction medium at a temperature above about 100xc2x0 C. but lower than about 220xc2x0 C., preferably between about 150 to about 200xc2x0 C.
The addition polymers of the present invention can be prepared via standard free radical solution polymerization methods that are well-known by those skilled in the art. The monomers of Formulae I to V can be homopolymerized or copolymerized in the presence of maleic anhydride. Free radical polymerization techniques are set forth in the Encyclopedia of Polymer Science, John Wiley and Sons, 13, 708 (1988).
Alternatively, and preferably, the monomers of this invention are polymerized in the presence of a single or multicomponent catalyst system comprising a Group VIII metal ion source (preferably palladium or nickel). Surprisingly, it has been found that the addition polymers so produced possess excellent transparency to deep UV light (193 nm) and exhibit excellent resistance to reactive ion etching.
The preferred polymers of this invention are polymerized from reaction mixtures comprising at least one polycyclic monomer selected from Formulae I and II, a solvent, a catalyst system containing a Group VIII metal ion source, and an optional chain transfer agent. The catalyst system can be a preformed single component Group VIII metal based catalyst or a multicomponent Group VIII metal catalyst.
Single Component Systems
In one embodiment, the single component catalyst system of this invention comprises a Group VIII metal cation complex and a weakly coordinating counteranion as represented by the following formula: 
wherein L represents a ligand containing 1, 2, or 3 xcfx80-bonds; M represents a Group VIII transition metal; X represents a ligand containing 1 "sgr"-bond and between 0 to 3 xcfx80-bonds; y is 0, 1, or 2 and z is 0 or 1 and wherein y and z cannot both be 0 at the same time, and when y is 0, a is 2 and when y is 1, a is 1; and CA is a weakly coordinating counteranion.
The phrase xe2x80x9cweakly coordinating counteranionxe2x80x9d refers to an anion which is only weakly coordinated to the cation, thereby remaining sufficiently labile to be displaced by a neutral Lewis base. More specifically the phrase refers to an anion which when functioning as a stabilizing anion in the catalyst system of this invention does not transfer an anionic substituent or fragment thereof to the cation, thereby forming a neutral product. The counteranion is non-oxidative, non-reducing, non-nucleophilic, and relatively inert.
L is a neutral ligand that is weakly coordinated to the Group VIII metal cation complex. In other words, the ligand is relatively inert and is readily displaced from the metal cation complex by the inserting monomer in the growing polymer chain. Suitable xcfx80-bond containing ligands include (C2 to C12) monoolefinic (e.g., 2,3-dimethyl-2-butene), dioolefinic (C4 to C12) (e.g., norbornadiene) and (C6 to C20) aromatic moieties. Preferably ligand L is a chelating bidentate cyclo(C6 to C12) diolefin, for example cyclooctadiene (COD) or dibenzo COD, or an aromatic compound such as benzene, toluene, or mesitylene.
Group VIII metal M is selected from Group VIII metals of the Periodic Table of the Elements. Preferably M is selected from the group consisting of nickel, palladium, cobalt, platinum, iron, and ruthenium. The most preferred metals are nickel and palladium.
Ligand X is selected from (i) a moiety that provides a single metal-carbon "sgr"-bond (no xcfx80 bonds) to the metal in the cation complex or (ii) a moiety that provides a single metal carbon "sgr"-bond and 1 to 3 xcfx80-bonds to the metal in the cation complex. Under embodiment (i) the moiety is bound to the Group VIII metal by a single metal-carbon "sgr"-bond and no xcfx80-bonds. Representative ligands defined under this embodiment include (C1 to C10) alkyl moieties selected from methyl, ethyl, linear and branched moieties such as propyl, butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl and (C7 to C15) aralkyl such as benzyl. Under embodiment (ii) generally defined above, the cation has a hydrocarbyl group directly bound to the metal by a single metal-carbon "sgr"-bond, and also by at least one, but no more than three xcfx80-bonds. By hydrocarbyl is meant a group that is capable of stabilizing the Group VIII metal cation complex by providing a carbon-metal "sgr"-bond and one to three olefinic xcfx80-bonds that may be conjugated or non-conjugated. Representative hydrocarbyl groups are (C3 to C20) alkenyl which may be non-cyclic, monocyclic, or polycyclic and can be substituted with linear and branched (C1 to C20) alkoxy, (C6 to C15) aryloxy or halo groups (e.g., Cl and F).
Preferably X is a single allyl ligand, or, a canonical form thereof, which provides a "sgr"-bond and a xcfx80-bond; or a compound providing at least one olefinic xcfx80-bond to the metal, and a "sgr"-bond to the metal from a distal carbon atom, spaced apart from either olefinic carbon atom by at least two carbonxe2x80x94carbon single bonds (embodiment iii).
It should be readily apparent to those skilled in the art that when ligand L or X is absent (i.e., y or z is zero), the metal cation complex will be weakly ligated by the solvent in which the reaction was carried out. Representative solvents include but are not limited to halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and aromatic solvents such as benzene, toluene, mesitylene, chlorobenzene, and nitrobenzene, and the like. A more detailed discussion on appropriate solvents will follow.
Selected embodiments of the Group VIII metal cation complexes of the single component catalyst systems of this invention are shown below.
Structure VII illustrates embodiment (i) wherein ligand X is a methyl group that is bound to the metal via a single metal-carbon "sgr"-bond, and ligand L is COD that is weakly coordinated to the palladium metal via two olefinic xcfx80-bonds. In the structure below M preferably represents palladium or nickel. 
Structures VIII, IX, and X illustrate various examples of embodiment (ii) wherein X is an allyl group that is bound to the metal (palladium is shown for illustrative purposes only) via a single metal-carbon "sgr"-bond and at least one but no more than three xcfx80-bonds.
In Structure VIII, L is not present but an aromatic group providing three xcfx80-bonds is weakly coordinated to the palladium metal; X is an allyl group providing a single metal-carbon "sgr"-bond and an olefinic xcfx80-bond to the palladium.
In Structure IX, L is COD and X is an allyl group providing a metal-carbon "sgr"-bond and an olefinic xcfx80-bond to the palladium.
Structure X illustrates an embodiment wherein ligand X is an unsaturated hydrocarbon group that provides a metal-carbon "sgr"-bond, a conjugated xcfx80-bond and two additional xcfx80-bonds to the palladium; L is absent. 
Substituents R20, R21, R22 will be described in detail below.
Structures XI and XII illustrate examples of embodiment (iii) wherein L is COD and X is a ligand that provides at least one olefinic xcfx80-bond to the Group VIII metal and a "sgr"-bond to the metal from a distal carbon atom, spaced apart from either olefinic carbon atom by at least two carbonxe2x80x94carbon single bonds. 
The above-described Group VIII cation complexes are associated with a weakly coordinating or non-coordinating counteranion, CAxe2x88x92, which is relatively inert, a poor nucleophile and provides the cation complex with essential solubility in the reaction solvent. The key to proper anion design requires that it be labile, and stable and inert toward reactions with the cationic Group VIII metal complex in the final catalyst species and that it renders the single component catalyst soluble in the solvents of this invention. The anions which are stable toward reactions with water or Brxc3x8nsted acids, and which do not have acidic protons located on the exterior of the anion (i.e., anionic complexes which do not react with strong acids or bases) possess the stability necessary to qualify as a stable anion for the catalyst system. The properties of the anion which are important for maximum lability include overall size, and shape (i.e., large radius of curvature), and nucleophilicity.
In general, a suitable anion may be any stable anion which allows the catalyst to be dissolved in a solvent of choice, and has the following attributes: (1) the anion should form stable salts with the aforementioned Lewis acid, Brxc3x8nsted acids, reducible Lewis Acids, protonated Lewis bases, thallium and silver cations; (2) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; (3) the anion should be a relatively poor nucleophile; and (4) the anion should not be a powerful reducing or oxidizing agent.
Anions that meet the foregoing criteria can be selected from the group consisting of a tetrafluoride of Ga, Al, or B; a hexafluoride of P, Sb, or As; perfluoro-acetates, propionates and butyrates, hydrated perchlorate; toluene sulfonates, and trifluoromethyl sulfonate; and substituted tetraphenyl borate wherein the phenyl ring is substituted with fluorine or trifluoromethyl moieties. Selected examples of counteranions include BF4xe2x88x92, PF6xe2x88x92, AlF3O3SCF3xe2x88x92, SbF6xe2x88x92, SbF5SO3Fxe2x88x92, AsF6xe2x88x92, trifluoroacetate (CF3CO2xe2x88x92), pentafluoropropionate (C2F5CO2xe2x88x92), heptafluorobutyrate (CF3CF2CF2CO2xe2x88x92), perchlorate (ClO4xe2x88x92.H2O), p-toluene-sulfonate (p-CH3C6H4SO3xe2x88x92) and tetraphenyl borates represented by the formula: 
wherein Rxe2x80x3 independently represents hydrogen, fluorine and trifluoromethyl and n is 1 to 5.
A preferred single component catalyst of the foregoing embodiment are represented by the formula: 
The catalyst comprises a xcfx80-allyl Group VIII metal complex with a weakly coordinating counteranion. The allyl group of the metal cation complex is provided by a compound containing allylic functionality which functionality is bound to the M by a single carbon-metal "sgr"-bond and an olefinic xcfx80-bond. The Group VIII metal M is preferably selected from nickel and palladium with palladium being the most preferred metal. Surprisingly, it has been found that these single component catalysts wherein M is palladium and the cation complex is devoid of ligands other than the allyl functionality (i.e., Ly=0), exhibit excellent activity for the polymerization of functional polycyclic monomers such as the silyl containing monomers of this invention. As discussed above, it will be understood that the catalysts are solvated by the reaction diluent which diluent can be considered very weak ligands to the Group VIII metal in the cation complex.
Substituents R20, R21, and R22 on the allyl group set forth above in Structures VIII, IX and XIII are each independently hydrogen, branched or unbranched (C1 to C5) alkyl such as methyl, ethyl, n-propyl, isopropyl, and t-butyl, (C6 to C14) aryl, such as phenyl and naphthyl, (C7 to C10) aralkyl such as benzyl, xe2x80x94COOR16, xe2x80x94(CH2)nOR16, Cl and (C5 to C6) cycloaliphatic, wherein R16 is (C1 to C5) alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and i-butyl, and n is 1 to 5.
Optionally, any two of R20, R21, and R22 may be linked together to form a cyclic- or multi-cyclic ring structure. The cyclic ring structure can be carbocyclic or heterocyclic. Preferably any two of R20, R21, and R22 taken together with the carbon atoms to which they are attached form rings of 5 to 20 atoms. Representative heteroatoms include nitrogen, sulfur and carbonyl. Illustrative of the cyclic groups with allylic functionality are the following structures: 
wherein R23 is hydrogen, linear or branched (C1 to C5) alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and pentyl, R24 is methylcarbonyl, and R25 is linear or branched (C1 to C20) alkyl. Counteranion CAxe2x88x92 is defined as above.
Additional examples of xcfx80-allyl metal complexes are found in R. G. Guy and B. L. Shaw, Advances in Inorganic Chemistry and Radiochemistry, Vol. 4, Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer, M. L. H. Green, R. B. King, R. Kxc3x6ster, P. L. I. Nagy, G. N. Schrauzer, Advances in Organometallic Chemistry, Vol. 2, Academic Press Inc., New York, 1964; W. T. Dent, R. Long and A. J. Wilkinson, J. Chem. Soc., (1964) 1585; and H. C. Volger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225; which are all hereby incorporated by reference.
The single component catalyst of the-foregoing embodiment can be prepared by combining a ligated Group VIII metal halide component with a salt that provides the counteranion for the subsequently formed metal cation complex. The ligated Group VIII metal halide component, counteranion providing salt, and optional xcfx80-bond containing component, e.g., COD, are combined in a solvent capable of solvating the formed single component catalyst. The solvent utilized is preferably the same solvent chosen for the reaction medium. The catalyst can be preformed in solvent or can be formed in situ in the reaction medium.
Suitable counteranion providing salts are any salts capable of providing the counteranions discussed above. For example, salts of sodium, lithium, potassium, silver, thallium, and ammonia, wherein the anion is selected from the counteranions (CAxe2x88x92) defined previously. Illustrative counteranion providing salts include TlPF6, AgPF6, AgSbF6, LiBF4, NH4 PF6, KAsF6, AgC2F5CO2, AgBF4AgCF3CO2, AgClO4.H2O, AgAsF6, AgCF3CF2CF2CO2, AgC2F5CO2, (C4H9)4NB(C6F5)4, and 
The specific catalyst: [allyl-Pd-COD]+PF6xe2x88x92 is preformed by forming a ligated palladium halide component, i.e., bis(allyl Pd bromide), which is then subjected to scission with a halide abstracting agent in the form of a counteranion providing salt, i.e., TlPF6 in the presence of COD. The reaction sequence is written as follows: 
When partitioned, only one COD ligand remains, which is bonded by two xcfx80-bonds to the palladium. The allyl functionality is bonded by one metal-carbon "sgr"-bond and one xcfx80-bond to the palladium.
For the preparation of the preferred xcfx80-allyl Group VIII metal/counteranion single component catalysts represented in Structure XIII above, i.e., when M is palladium, allylpalladium chloride is combined with the desired counteranion providing salt, preferably silver salts of the counteranion, in an appropriate solvent. The chloride ligand comes off the allyl palladium complex as a precipitate of silver chloride (AgCl) which can be filtered out of the solution. The allylpalladium cation complex/counteranion single component catalyst remains in solution. The palladium metal is devoid of any ligands apart from the allylic functionality.
An alternative single component catalyst that is useful in the present invention is represented by the formula below:
Pd[R27CN]4[CAxe2x88x92]2 
wherein R27 independently represents linear and branched (C1 to C10) alkyl and CAxe2x88x92 is a counteranion defined as above.
Preformed single component catalyst system useful in making polymers utilized in this invention is represented by the formula:
EnM(Q)f(Rz)g 
M is a Group VIII transition metal preferably selected from nickel, palladium, platinum, iron, rhodium and cobalt. Q is an electron withdrawing ligand preferably selected from linear and branched (C1 to C10) perhaloalkyl, (C7 to C24) perhaloalkaryl and perhaloaryl, n is an integer of 0, 1, 2 or 3; f is 1, 2, or 3 with the proviso that when M is rhodium f must be 3; and g is an integer of 0 or 1, when f is 1 Rz must be present. The perhaloalkyl ligands are preferably selected from trifluoromethyl, perfluoroethyl and perfluoroethyl. The perhaloaryl ligands are preferably selected from pentafluorophenyl, pentachlorophenyl, and pentabromophenyl groups. The peralkaryl ligand is preferably 2,4,6-tris(trifluoromethylphenyl). E is selected from a monodentate or bidentate ligand.
Examples of monodentate ligands include xcfx80-arenes such as benzene, toluene, and mesitylene; ethers, polyethers such as glme, diglyme, triglyme, tetraglyme and thioethers represented by the formulae Rixe2x80x94Oxe2x80x94Ri and Rixe2x80x94Sxe2x80x94Ri wherein Ri can be the same or different and represents a linear and branched (C1 to C10) alkyl group, the Ri groups that are connected to the heteroatom can be taken together to represent heterocyclic ring containing 4 to 8 carbon atoms, representative ethers include methyltertbutylether, diethylether, furan, tetrahydrofuran, representative thioethers include thiophene, tetrahydrothiophene; cyclic diethers such as dioxane; ketones represented by the formula Ri xe2x80x94C(O)xe2x80x94Ri wherein Ri is as defined above and the Ri groups connected to the carbonyl moiety can be taken together to form a substituted or unsubstituted cyclic ketone containing 5 to 8 carbon atoms, substituents include linear or branched (C1 to C10) alkyl and (C6 to C24) aryl, representative ketones include acetone, methylethylketone and methylphenylketone; amines of the formula N(Rd)3 wherein Rd independently represents linear or branched (C1 to C10) alkyl, (C7 to C10) aralkyl such as benzyl, (C6 to C24) aryl and cycloaliphatic groups containing 5 to 8 carbon atoms, the alkyl, aryl and cycloaliphatic substituents optionally contain halogen atoms selected from chlorine, bromine, fluorine and iodine, representative amines include triethylamine, tripropylamine and tributylamine; pyridine, linear and branched (C1 to C10) alkyl group substituted pyridines; phosphines of the formula P(Rd)3 wherein Rd is as defined above including alkylphosphines, arylphosphines and alkarylphosphines with trialkyl, triperfluoroalkyl, and triarylphosphines being preferred; alkylphosphine oxides, arylphosphine oxides, and alkarylphosphine oxides of the formula (Rd)3PO wherein Rd is as defined above, preferred are the trialkyl triperfluoroalkyl, and triarylphosphine oxides; alkylphosphites, arylphosphites and alkarylphosphites of the formula P(ORd)3 wherein Rd is as defined above, preferred are the trialkyl, triperfluoroalkyl and triarylphosphites; esters of the formula RiC(O)ORi wherein R1 is defined above and wherein the Ri substituents bonded to the carbonyl and oxygen atom can be taken together therewith to form an unsubstituted or substituted lactone ring containing 3 to 8 carbon atoms, representative esters include ethyl acetate, representative lactones include xcex2-propiolactone and xcex3-butyrolactone. Rz represents a substituted or unsubstituted allyl ligand set forth below: 
wherein R20, R21, and R22 are as previously defined.
A representative preformed catalyst that contains no ligands other than the electron withdrawing group ligand is bis(2,4,6-tris(trifluoromethylphenyl)) nickel.
Representative preformed catalysts containing monodentate ligands are (toluene)bis(perfluorophenyl) nickel, (mesitylene)bis(perfluorophenyl) nickel, (benzene)bis(perfluorophenyl) nickel, bis(tetrahydrofuran)bis(perfluorophenyl) nickel, (dimethoxyethane)bis(2,4,6-tris(trifluoromethylphenyl)) nickel, bis(dioxane)bis(perfluorophenyl) nickel, (methallyl)nickel(pentafluorophenyl)(triphenylphosphine), and (methallyl)nickel(pentafluorophenyl)(tricyclohexylphosphine), and the compound [Ni(C6F5)2Cl]22xe2x80x94.
Examples of bidentate ligands include hemilabile chelating ligands containing phosphorus, oxygen, nitrogen and sulfur represented by the formula 
wherein Y and Z independently represent phosphorus, oxygen, carbonyl, nitrogen and sulfur and K is an unsubstituted and substituted hydrocarbon backbone moiety containing from 2 to 25 carbon atoms or a divalent alkylene ether moiety wherein the alkylene radicals independently contain 1 to 10 carbon atoms. The phosphorus, oxygen, sulfur, nitrogen atoms and the carbonyl carbon can optionally be substituted with linear and branched(C1 to C10) alkyl and (C6 to C24) aryl groups. The hydrocarbon backbone moiety can be substituted with pendant linear and branched alkyl groups containing 1 to 10 carbon atoms, alicyclic groups of 5 to 15 carbon atoms, aryl groups of containing 6 to 20 carbon atoms, and amines. The pendant substituents on the hydrocarbon backbone can optionally be substituted with linear and branched (C1 to C10) alkyl, phenyl groups, halides, and amino groups. Catalysts of the invention containing the above described bidentate ligands can be represented by the formula 
wherein K, Y, Z, M, and Q are as defined above. Illustrative of the catalysts containing bidentate chelating ligands where Y and Z are phosphorus, oxygen or carbonyl are represented by the formulae 
wherein Rh independently represents hydrogen, linear and branched(C1 to C10) alkyl and (C6 to C24) aryl and Rj represents linear and branched(C1 to C10) alkyl and (C6 to C24) aryl.
The ratio of monomer to catalyst in the reaction medium can range from about 50,000:1 to about 50:1, preferably from about 20,000:1 to about 100:1, more preferably from about 2000:1 to about 100:1, and most preferably from about 500:1 to about 100:1. The reaction can be run in the organic solvents, specified hereinabove. Preferred solvents include the previously described aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane and aromatic hydrocarbons such as benzene, toluene and mesitylene as well as polar organic hydrocarbons which are described below. The foregoing solvents can be used alone or in mixtures of two or more. Polar organic solvents include the ethers, esters and ketones described as ligands in the description of the catalyst formula set forth immediately above. Suitable polar organic solvents include ethyl acetate, methyltertbutylether, diethylether, tetrahydrofuran, dioxane, acetone, methylethylketone, methylphenylketone, xcex2-propiolactone and xcex3-butyrolactone. The reaction temperature employed can range from about 0xc2x0 C. to about 70xc2x0 C., preferably from about 10xc2x0 C. to about 50xc2x0 C., and more preferably from about 20xc2x0 C. to about 40xc2x0 C. The preferred concentration of monomer in reaction solvent or diluent ranges from about 5 weight percent monomer in solvent to about to about 50 weight percent.
When employing the preformed catalyst systems of the formula EnM(Q)f(Rz)g, it has been found that effective reduction of molecular weight of the polymer product can be attained by in increasing the catalyst concentration in the monomer along with decreasing the concentration of monomer in reaction solvent. We have found a relative effect between catalyst concentration and monomer concentration in the reaction medium. When operating within the preferred monomer to catalyst ratios and monomer to reaction solvent ranges an increase in catalyst loading with a concomitant decrease in monomer to solvent concentration a reduction in the molecular weight of the polymer product is observed. We have also observed that by conducting the polymerization reaction in the presence of a dual component solvent system while maintaining a relatively high catalyst to monomer and monomer to solvent concentration provides an effective reduction in molecular weight of the polymer product. By dual component solvent system is meant that a non-polar hydrocarbon diluent such as cyclohexane is used in combination with a polar organic solvent such as ethyl acetate. Suitable non-polar solvents include any solvent that is a diluent, i.e., miscible with the polar organic solvent. The polar organic solvents are preferably organic esters that are suitable solvents for the catalyst component. The ratio of non-polar hydrocarbon solvent to polar organic solvent can range from 75:25 w/w to 25:75 w/w with 50:50 w/w being preferred. The dual component solvent system method of molecular weight reduction is advantageous from the standpoint of allowing for higher concentrations of monomer to be employed in the reaction medium.
The preformed single component catalysts of the above formula can be synthesized via several routes. In one synthesis route a Group VIII metal ion source, e.g., nickel trifluoroacetate, is reacted with a reagent (e.g., bis(pentafluorophenyl) zinc, or a Grignard reagent such as pentafluorophenyl magnesium bromide) that is capable of transferring the appropriate electron withdrawing ligand to the Group VIII metal. The reaction is conducted in an appropriate solvent such as diethylether or THF. The solvent system can provide the source of the remaining ligand(s). For example, if THF is employed as the solvent, the catalyst product of the synthesis is (THF)2Ni(C6F5)2. The synthesis can be conducted in a temperature range of from about xe2x88x92100xc2x0 C. to about 100xc2x0 C. Typically the reaction can be conducted at room temperature but elevated temperatures can be employed to increase the rate of reaction. In another synthesis route the THF ligand on the catalyst can be substituted by a mono- or bidentate ligand such as toluene or triphenyl phosphine simply by reacting the (THF)2Ni(C6F5)2 catalyst with toluene or triphenylphosphine. Representative reaction schemes are set forth below. 
In an alternate synthesis route a reagent containing the Group VIII metal compound containing the desired the mono- or bidentate ligand can be reacted with a reagent containing the electron withdrawing group ligand. For example, bis(triphenylphosphine) nickel dibromide can be reacted in a suitable solvent with the Grignard reagent, pentafluorophenyl magnesium bromide, to give the catalyst ((C6H5)3P)2Ni(C6F5)2. The reaction scheme is represented below. 
In another method for preparing the preformed catalyst, a neutral (zero oxidation state) Group VIII metal reagent, e.g., Ni(COD)2, in combination with an appropriate ligand reagent (e.g., THF) is reacted in a solvent with an electron withdrawing group ligand reagent capable of undergoing oxidative addition to the Group VIII metal. Pentafluorobenzoyl chloride can be employed as an electron withdrawing ligand reagent. The reaction scheme is set forth below. 
In another synthesis route the catalyst can be prepared via the metal vapor and activated metal synthesis procedure described by R. G. Gastinger, B. B. Anderson, K. J. Klabunde, J. Am. Chem. Soc. 1980, 102, 4959-4966 and R. D. Rieke, W. J. Wolf, N. Kujundzic, A. V. Kavaliunas, J. Am. Chem. Soc. 1977, 99, 4159-4160, respectively. The electron withdrawing ligand reagent undergoes oxidative addition to the activated zero valent Group VIII metal to form the preformed catalyst.
It is to be understood that the catalysts described under the formula EnM(Q)f(Rz)g above can be prepared in situ by reacting a Group VIII metal containing (M) reagent with the desired electron withdrawing ligand (Q) reagent and the mono- and bidentate ligand (E) reagent in the presence of the monomer solution in the reaction medium. Alternatively, these catalysts are prepared in situ by arylating or alkylating the Group VIII metal in the optional presence of activating agents. The Group VIII metal containing reagents can be selected from a compound containing nickel, palladium, platinum cobalt, iron, and rhodium, with nickel and palladium being most preferred. There are no restrictions on the Group VIII metal compound so long as the compound provides a source of Group VIII metal ions that are capable of being arylated or alkylated. In other words, the Group VIII metal containing moiety should contain groups or ligands that can be easily displaced by the electron withdrawing ligand provided by the arylation or alkylation agent. Preferably, the Group VIII metal compound is soluble or can be made to be soluble (by the attachment of appropriate ligands) in the reaction medium. Examples of reagents containing the Group VIII metal include anionic ligands selected from the halides such as chloride, bromide, iodide or fluoride ions; pseudohalides such as cyanide, cyanate, thiocyanate, hydride; carbanions such as branched and unbranched (C1 to C40) alkylanions, phenyl anions; cyclopentadienylide anions; xcfx80-allyl groupings; enolates of xcex2-dicarbonyl compounds such as acetylacetonate (4-pentanedionate), 2,2,6,6-tetramethyl-3,5-heptanedionate, and halogenated acetylacetonoates such as 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-2,4-pentanedionate; anions of acidic oxides of carbon such as carboxylates and halogenated carboxylates (e.g., acetates, 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) and oxides of nitrogen (e.g., nitrates, nitrites, etc.) of bismuth (e.g., bismuthate, etc.), of aluminum (e.g., aluminates, etc.), of silicon (e.g., silicate, etc.), of phosphorous (e.g., phosphates, phosphites, phosphines, etc.) of sulfur (e.g., sulfates such as triflate, p-toluene sulfonate, sulfites, etc.); ylides; amides; imides; oxides; phosphides; sulfides; (C6 to C24) aryloxides, (C1 to C20) alkoxides, hydroxide, hydroxy (C1 to C20) alkyl; catechols; oxalate; chelating alkoxides and aryloxides.
Examples of Group VIII transition metal compounds suitable as the Group VIII metal ion source include: palladium ethylhexanoate, trans-Pd Cl2(PPh3)2, palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate)2(PPh3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride, nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh2CH2)2, (P(cyclohexyl)3)H Ni(Ph2P(C6H4)CO2), (PPh3) (C6H5)Ni(Ph2PCHxe2x95x90C(O)Ph), bis(2,2,6,6-tetramethyl-3,5-heptanedionate) nickel (II), nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, cobalt neodecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, iron naphthenate, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, rhodium chloride, rhodium tris(triphenylphosphine) trichloride.
The arylating or alkylating agent or cocatalyst contains perhalophenyl and 2,4,6-tris(trifluoromethylphenyl) moieties. Preferred cocatalysts or arylation and alkylation agents include bis(pentahalophenyl)zinc-dimethoxyethane (e.g., (C6X5)2Zn.dme) where X represents a halogen substituent, preferably fluorine, bromine and chlorine, and dme is dimethoxyethane, tris(perfluorophenyl)boron (e.g., B(C6F5)3), tris(perfluorophenyl)boron hydrate (e.g., B(C6F5)3.3H2O) tris(2,4,6-trifluoromethyl) phenyl lithium, bis(2,4,6-trifluoromethyl) phenyl zinc, bis(2,4,6-trifluoromethyl) phenyl magnesium, and bis(trifluoromethyl)cadmium.dme (e.g., Cd(CF3)2.dme).
Activating agents include trialkyl aluminum compounds such as triethylaluminum, dialkylmagnesium compounds such as dibutylmagnesium, dialkylzinc such as diethylzinc. We have found that for most of the catalyst systems these activators increase the rate of initiation of the polymerization reaction. When aluminum alkyls are employed as activators, it is preferable that an oxygen containing compound is employed therewith. Suitable oxygen containing compounds can be selected from tetraethoxysilane, dimethyldiethoxysilane, diethylether, propanol or monomers of the invention that contain oxygen substituents. When aluminum alkyls are employed as the activator there is no need to add an oxygen containing compound so long as the cyclic monomer(s) to be polymerized bears an oxygen containing substituent such as an carboxylic acid, ester, carbonyl, ether, or alcohol containing substituent. When utilizing non-polar hydrocarbon solvents, e.g., hexane, cyclohexane, toluene, etc., as the reaction diluent, relatively small amounts of the oxygen containing compounds are employed (about 10 moles of oxygen containing compound per mole of Group VIII metal). When halohydrocarbon diluents, e.g., dichloromethane, dichloroethane, etc., are used in the polymerization, higher levels of oxygen containing compound (up to about 1000 moles of oxygen containing compound per mole of Group VIII metal) are employed in the reaction medium.
We have found that the Group IVB metals, preferably, titanium, zirconium and hafnium; the lanthanide series metals, preferably, samarium and europium; the Group VB metals, preferably, vanadium; and the Group VA metals, preferably, silicon, germanium, tin and lead can be arylated in situ to form active catalysts for cyclic olefin polymerzation. These metals include ligands such as halide groups, acetate groups and acetoacetonate groups that are easily displaced by the aryl groups provided by the arylating or alkylating agent described above.
In addition to being effective catalysts for the addition polymerization of monomers suitable for photoresist polymer applications, the above described catalysts are suitable for polymerizing many types of substituted and unsubstituted cyclic olefin monomer classes. Preformed or in situ prepared catalysts of the formula EnM(Q)f(Rz)g are useful for polymerizing any combination of monomers of Formulae I, II, III, IV and V defined above. Further to the cyclic olefin monomers of described under Formulae I to V, we have found that these catalysts are useful for polymerizing cyclic olefin monomers of Formulae VI and VII set forth below: 
wherein R30, R31, R32, and R33 independently represent hydrogen, linear or branched (C1 to C20) alkyl, (C6 to C24) aryl and at least one of R30 to R33 representing the group xe2x80x94B)nxe2x80x94SiR34R35R36 wherein B is a divalent bridging or spacer radical and n is an integer of 0 or 1. The divalent radical is an alkylene group represented by the formula xe2x80x94(CdH2d)xe2x80x94 where d represents the number of carbon atoms in the alkylene chain and is an integer from 1 to 10. The divalent radicals are preferably selected from linear and branched (C1 to C10) alkylene such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. When branched alkylene radicals are contemplated, it is to be understood that a hydrogen atom in the linear alkylene chain is replaced with a linear or branched (C1 to C5) alkyl group. When n is 0 it should be apparent that the spacer radical is not present and B represents a covalent bond. In other words the silyl group, xe2x80x94SiR34R35R36, is attached directly to the cyclic ring. Substituents R34, R35, and R36 independently represent halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, linear or branched (C1 to C20) alkyl, linear or branched (C1 to C20) alkoxy, substituted or unsubstituted (C6 to C20) aryloxy, linear or branched (C1 to C20) alkyl carbonyloxy, and (C1 to C20) alkyl peroxy. Preferably, at least one of R34, R35, or R36 is selected from a linear or branched (C1 to C10) alkoxy group or a halogen group. More preferably, each of R34, R35, and R36 are the same and are selected from methoxy, ethoxy, propoxy, butoxy, pentoxy, and chlorine groups. Still more preferably, n is 0, and R34, R35 and R36 are ethoxy, e.g., at least one of R30 to R33 is a triethoxysilyl substituent.
In another embodiment, the arylated and alkylated catalysts of the formula EnM(Q)f(Rz)g are useful to homo- and copolymerize one or more monomers of the monomer formula 
wherein R40, R41, R42, and R43 independently represent hydrogen, linear and branched (C1 to C20) alkyl, hydrocarbyl substituted and unsubstituted (C5 to C12) cycloalkyl, (C7 to C15) aralkyl, (C3 to C20) alkynyl, linear and branched (C3 to C20) alkenyl, vinyl; any of R40 and R41 or R42 and R43 can be taken together to form a (C1 to C10) alkylidenyl group, R40 and R43 can be taken together with the two ring carbon atoms to which they are attached can represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, or an anhydride or dicarboxyimide group; xe2x80x94(B)nxe2x80x94SiR34R35R36 wherein B is a divalent bridging or spacer radical selected from linear and branched (C1 to C10) alkylene, n is an integer of 0 or 1, R34, R35, and R36 independently represent halogen, linear or branched (C1 to C20) alkyl, linear or branched (C1 to C20) alkoxy, substituted or unsubstituted (C6 to C20) aryloxy, linear or branched (C1 to C20) alkyl carbonyloxy, and (C1 to C20) alkyl peroxy; xe2x80x94(A)nxe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94ORxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)Rxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Rxe2x80x3, xe2x80x94(A)nxe2x80x94OCH2C(O)OR*, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x94OCH2C(O)OR*, xe2x80x94(A)nxe2x80x94OC(O)C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94Oxe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94OC(O)xe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)xe2x80x94Axe2x80x2xe2x80x94ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94OC(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94Oxe2x80x94Axe2x80x2xe2x80x94C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(O)Oxe2x80x94Axe2x80x2xe2x80x94OC(O)C(O)ORxe2x80x3, xe2x80x94(A)nxe2x80x94C(Rxe2x80x3)2CH(Rxe2x80x3)(C(O)ORxe2x80x3), and xe2x80x94(A)nxe2x80x94C(Rxe2x80x3)2CH(C(O)ORxe2x80x3)2, xe2x80x94(A)nxe2x80x94Rxe2x80x3
wherein R37 is hydrogen, linear and branched (C1 to C10) alkyl, or (C6 to C15) aryl, wherein n is 0 or 1, m is an integer from 0 to 5, xe2x80x94Axe2x80x94 and xe2x80x94Axe2x80x2xe2x80x94 independently represent a divalent radical selected from the group consisting of linear and branched (C1 to C10) alkylene, (C2 to C10) alkylene ethers, polyethers, or a cyclic group of the formula: 
wherein a is an integer from 2 to 7, Rxe2x80x3 represents hydrogen or linear and branched (C1 to C10) alkyl, xe2x80x94C(CH3)3, xe2x80x94Si(CH3)3, xe2x80x94(CH(Rp)OCH2CH3, xe2x80x94(CH(Rp)OC(CH3)3, 
wherein Rp represents hydrogen or a linear or branched (C1 to C5) alkyl group; linear and branched (C1 to C10) alkoxyalkylene, polyethers, monocyclic and polycyclic (C4 to C20) cycloaliphatic moieties, cyclic ethers, cyclic diethers, cyclic ketones, and cyclic esters (lactones), when any of R40 to R43 represent a succinic or carboxyimide moiety and n is 1 A can only represent a linear or branched (C1 to C10) alkylene group.
Accordingly, homopolymers and copolymers comprising repeating units polymerized from one or more of the monomers of Formulae I to VI can be easily prepared.
Multicomponent Systems
The multicomponent catalyst system embodiment of the present invention comprises a Group VIII metal ion source, in combination with one or both of an organometal cocatalyst and a third component. The cocatalyst is selected from organoaluminum compounds, dialkylaluminum hydrides, dialkyl zinc compounds, dialkyl magnesium compounds, and alkyllithium compounds.
The Group VIII metal ion source is preferably selected from a compound containing nickel, palladium, cobalt, iron, and ruthenium with nickel and palladium being most preferred. There are no restrictions on the Group VIII metal compound so long as it provides a source of catalytically active Group VIII metal ions. Preferably, the Group VIII metal compound is soluble or can be made to be soluble in the reaction medium.
The Group VIII metal compound comprises ionic and/or neutral ligand(s) bound to the Group VIII metal. The ionic and neutral ligands can be selected from a variety of monodentate, bidentate, or multidentate moieties and combinations thereof.
Representative of the ionic ligands that can be bonded to the metal to form the Group VIII compound are anionic ligands selected from the halides such as chloride, bromide, iodide or fluoride ions; pseudohalides such as cyanide, cyanate, thiocyanate, hydride; carbanions such as branched and unbranched (C1 to C40) alkylanions, phenyl anions; cyclopentadienylide anions; xcfx80-allyl groupings; enolates of xcex2-dicarbonyl compounds such as acetylacetonate (4-pentanedionate), 2,2,6,6-tetramethyl-3,5-heptanedionate, and halogenated acetylacetonoates such as 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-2,4,-pentanedionate; anions of acidic oxides of carbon such as carboxylates and halogenated carboxylates (e.g., acetates, 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) and oxides of nitrogen (e.g., nitrates, nitrites, etc.) of bismuth (e.g., bismuthate, etc.), of aluminum (e.g., aluminates, etc.), of silicon (e.g., silicate, etc.), of phosphorous (e.g., phosphates, phosphites, phosphines, etc.) of sulfur (e.g., sulfates such as triflate, p-toluene sulfonate, sulfites, etc.); ylides; anides; imides; oxides; phosphides; sulfides; (C6 to C24) aryloxides, (C1 to C20) alkoxides, hydroxide, hydroxy (C1 to C20) alkyl; catechols; oxalate; chelating alkoxides and aryloxides. Palladium compounds can also contain complex anions such as PFxe2x88x926, AlF3O3SCFxe2x88x923, SbFxe2x88x926 and compounds represented by the formulae:
Al(Rxe2x80x2xe2x80x3)xe2x88x924, B(X)xe2x88x924 
wherein Rxe2x80x2xe2x80x3 and X independently represent a halogen atom selected from Cl, F, I, and Br, or a substituted or unsubstituted hydrocarbyl group. Representative of hydrocarbyl are (C1 to C25) alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonodecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, and isomeric forms thereof; (C2 to C25) alkenyl such as vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, pentacosenyl, and isomeric forms thereof. (C6 to C25) aryl such as phenyl, tolyl, xylyl, naphthyl, and the like; (C7 to C25) aralkyl such as benzyl, phenethyl, phenpropyl, phenbutyl, phenhexyl, napthoctyl, and the like; (C3 to C8) cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl, 2-norbornenyl, and the like. In addition to the above definitions X represents the radical: 
The term xe2x80x9csubstituted hydrocarbylxe2x80x9d means the hydrocarbyl group as previously defined wherein one or more hydrogen atoms have been replaced with a halogen atom such as Cl, F, Br, and I (e.g., as in the perfluorophenyl radical); hydroxyl; amino; alkyl; nitro; mercapto, and the like.
The Group VIII metal compounds can also contain cations such as, for example, organoammonium, organoarsonium, organophosphonium, and pyridinium compounds represented by the formulae: 
wherein A represents nitrogen, arsenic, and phosphorous and the R28 radical can be independently selected from hydrogen, branched or unbranched (C1 to C20) alkyl, branched or unbranched (C2 to C20) alkenyl, and (C5 to C16) cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. R29 and R30 are independently selected from hydrogen, branched and unbranched (C1 to C50) alkyl, linear and branched (C2 to C50) alkenyl and (C5 to C16) cycloalkyl groups as defined above; and n is 1 to 5, preferably n is 1, 2, or 3, most preferably n is 1. The R30 radicals preferably are attached to positions 3, 4, and 5 on the pyridine ring.
It should be noted that increasing the sum of the carbon atoms contained in the R28 radicals confers better solubility of the transition metal compound in organic media such as organic solvents and polycyclic the monomer. Preferably, the R28 radicals are selected from (C1 to C18) alkyl groups wherein the sum of carbon atoms for all R28 radicals is 15 to 72, preferably 25 to 48, more preferably 21 to 42. The R21 radical is preferably selected from linear and branched (C1 to C50) alkyl, more preferably (C10 to C40) alkyl. R30 is preferably selected from linear and branched (C1 to C40) alkyl, more preferably (C2 to C30) alkyl.
Specific examples of organoammonium cations include tridodecylammonium, methyltricaprylammonium, tris(tridecyl)ammonium and trioctylammonium. Specific examples of organoarsonium and organophosphonium cations include tridodecylarsonium and phosphonium, methyltricaprylarsonium and phosphonium, tris(tridecyl)arsonium and phosphonium, and trioctylarsonium and phosphonium. Specific pyridinium cations include eicosyl-4-(1-butylpentyl)pyridinium, docosyl-4-(13-pentacosyl)pyridinium, and eicosyl-4-(1-butylpentyl)pyridinium.
Suitable neutral ligands which can be bonded to the palladium transition metal are the olefins; the acetylenes; carbon monoxide; nitric oxide, nitrogen compounds such as ammonia, alkylisocyanide, alkylisocyanate, alkylisothiocyanate; pyridines and pyridine derivatives (e.g., 1,10-phenanthroline, 2,2xe2x80x2-dipyridyl), 1,4-dialkyl-1,3-diazabutadienes, 1,4-diaryl-1,3-diazabutadienes and amines such as represented by the formulae: 
wherein Rxe2x88x92is independently hydrocarbyl or substituted hydrocarbyl as previously defined and n is 2 to 10. Ureas; nitriles such as acetonitrile, benzonitrile and halogenated derivatives thereof-, organic ethers such as dimethyl ether of diethylene glycol, dioxane, tetrahydrofuran, furan diallyl ether, diethyl ether, cyclic ethers such as diethylene glycol cyclic oligomers; organic sulfides such as thioethers (diethyl sulfide); arsines; stibines; phosphines such as triarylphosphines (e.g., triphenylphosphine), trialkylphosphines (e.g., trimethyl, triethyl, tripropyl, tripentacosyl, and halogenated derivatives thereof), bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(dimethylphosphino)propane, bis(diphenylphosphino)butane, (S)-(xe2x88x92)2,2xe2x80x2-bis(diphenylphosphino)-1,1xe2x80x2-binaphthyl, (R)-(+)-2,2xe2x80x2-bis(diphenylphosphino)-1,1xe2x80x2-binaphthyl, and bis(2-diphenylphosphinoethyl)phenylphosphine; phosphine oxides, phosphorus halides; phosphites represented by the formula:
P(OR31)3 
wherein R31 independently represents a hydrocarbyl or substituted hydrocarbyl as previously defined; phosphorus oxyhalides; phosphonates; phosphonites, phosphinites, ketones; sulfoxides such as (C1 to C20) alkylsulfoxides; (C6 to C20) arylsulfoxides, (C7 to C40) alkarylsulfoxides, and the like. It should be recognized that the foregoing neutral ligands can be utilized as optional third components as will be described hereinbelow.
Examples of Group VIII transition metal compounds suitable as the Group VIII metal ion source include: palladium ethylhexanoate, trans-Pd Cl2(PPh3)2, palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate)2(PPh3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride, nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh2CH2)2, (P(cyclohexyl)3)H Ni(Ph2P(C6H4)CO2), (PPh3) (C6H5)Ni(Ph2 PCHxe2x95x90C(O)Ph), bis(2,2,6,6-tetramethyl-3,5-heptanedionate) nickel (II), nickel (II) hexafluoroacetylacetonate tetrahrydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahrydrate, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, cobalt neodecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, iron napthenate, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, ruthenium tris(triphenylphosphine) dichloride, ruthenium tris(triphenylphosphine) hydrido chloride, ruthenium trichloride, ruthenium tetrakis(acetonitrile) dichloride, ruthenium tetrakis(dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris(triphenylphosphine) trichloride.
The organoaluminum component of the multicomponent catalyst system of the present invention is represented by the formula:
AlR323xe2x88x92xQx 
wherein R32 independently represents linear and branched (C1 to C20) alkyl, (C6 to C24) aryl, (C7 to C20) aralkyl, (C3 to C10) cycloalkyl; Q is a halide or pseudohalide selected from chlorine, fluorine, bromine, iodine, linear and branched (C1 to C20) alkoxy, (C6 to C24) aryloxy; and x is 0 to 2.5, preferably 0 to 2.
Representative organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum, tris-2-norbornylaluminum, and the like; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and the like; monoalkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, isobutylaluminum dichloride, and the like; and alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, isobutylaluminum sesquichloride, and the like.
The dialkylaluminum hydride is selected from linear and branched (C1 to C10) dialkylaluminum hydride, with diisobutylaluminum hydride being a preferred dialkylaluminum hydride compound.
The dialkyl zinc compounds are selected from linear and branched (C1 to C10) dialkyl zinc compounds with diethyl zinc being preferred. The dialkyl magnesium compounds are selected from linear and branched (C1 to C10) dialkyl magnesium with dibutyl magnesium being the most preferred. The alkyl lithiums are selected from linear and branched (C1 to C10) alkyl lithium compounds. Butyllithium is the preferred alkyl lithium.
In the practice of the present invention, the catalytic system obtained from the Group VIII metal ion source is utilized with one or both of a component selected from the group of cocatalyst compounds, and third component compounds.
Examples of third components are Lewis acids such as the BF3.etherate, TiCl4, SbF5, tris(perfluorophenyl)boron, BCl3, B(OCH2CH3)3; strong Brxc3x8nsted acids such as hexafluoroantimonic acid (HSbF6), HPF6 hydrate, trifluoroacetic acid (CF3CO2H), and FSO3H.SbF5, H2C(SO2CF3)2 CF3SO3H, and paratoluenesulfonic acid; halogenated compounds such as hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutylester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil, i.e., 
electron donors such as phosphines and phosphites and olefinic electron donors selected from (C4 to C12) aliphatic and (C6 to C12) cycloaliphatic diolefins, such as butadiene, cyclooctadiene, and norbornadiene.
Acidity of strong Brxc3x8nsted acids can be gauged by determining their Hammett acidity function H0. A definition of the Hammett acidity function is found in Advanced Inorganic Chemistry by F. A. Cotton and G. Wilkinson, Wiley-Interscience, 1988, p. 107.
As set forth above the neutral ligands can be employed as optional third components with electron donating properties.
In one embodiment of the invention, the multicomponent catalyst system can be prepared by a process which comprises mixing the catalyst components, i.e., the Group VIII metal compound, the cocatalyst compound, and third component (if employed), together in a hydrocarbon or halohydrocarbon solvent and then mixing the premixed catalyst system in the reaction medium comprising at least one silyl functional polycyclic monomer. Alternatively, (assuming the optional third component is utilized), any two of the catalyst system components can be premixed in a hydrocarbon or halohydrocarbon solvent and then introduced into the reaction medium. The remaining catalyst component can be added to the reaction medium before or after the addition of the premixed components.
In another embodiment, the multicomponent catalyst system can be prepared in situ by mixing together all of the catalyst components in the reaction medium. The order of addition is not important.
In one embodiment of the multicomponent catalyst system of the present invention, a typical catalyst system comprises a Group VIII transition metal salt, e.g., nickel ethylhexanoate, an organoaluminum compound, e.g., triethylaluminum, and a mixture of third components, e.g., BF3.etherate and hexafluoroantimonic acid (HSbF6), in a preferred molar ratio of Al/BF3.etherate/Ni/acid of 10/9/1/0.5-2. The reaction scheme is written as follows:
1. nickel ethylhexanoate+HSbF6+9BF3.etherate+10 triethylaluminumxe2x86x92Active Catalyst
In another embodiment of the multicomponent catalyst system of the invention, the catalyst system comprises a nickel salt, e.g., nickel ethylhexanoate, an organoaluminum compound, e.g., triethylaluminum, and a third component Lewis acid, e.g., tris(perfluorophenyl)boron as shown in the following scheme:
2. nickel ethylhexanoate+tris(perfluorophenyl)boron+triethylaluminumxe2x86x92Active Catalyst
In another embodiment of the multicomponent catalyst system of the invention the third component is a halogenated compound selected from various halogenated activators. A typical catalyst system comprises a Group VIII transition metal salt, an organoaluminum, and a third component halogenated compound as shown below:
3. nickel ethylhexanoate+triethylaluminum+chloranilxe2x86x92Active Catalyst
In still another embodiment of the multicomponent catalyst system of this invention no cocatalyst is present. The catalyst system comprises a Group VIII metal salt (e.g. 3-allylnickelbromide dimer and a Lewis acid (e.g. tris(perfluorophenyl)boron as shown below:
4. xcex73-allylnickel chloride+tris(perfluorophenyl)boronxe2x86x92Active Catalyst
We have found that the choice of Group VIII metal in the metal cation complex of both the single and multicomponent catalyst systems of this invention influences the microstructure and physical properties of the polymers obtained. For example, we have observed that palladium catalysts typically afford norbornene units which are exclusively 2,3 enchained and showing some degree of tacticity. The polymers catalyzed by the type 2 catalyst systems and the single component catalyst systems of the formula EnNi(C6F5)2 described above contain a perfluorophenyl group at at least one of the two terminal ends of the polymer chain. In other words, a perfluorophenyl moiety can be located at one or both terminal ends of the polymer. In either case the perfluorophenyl group is covalently bonded to and pendant from a terminal polycyclic repeating unit of the polymer backbone.
Reactions utilizing the single and multicomponent catalysts of the present invention are carried out in an organic solvent which does not adversely interfere with the catalyst system and is a solvent for the monomer. Examples of organic solvents are aliphatic (non-polar) hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, chlorobenzene, o-dichlorobenzene, toluene, and xylenes; halogenated (polar) hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane.
The choice of reaction solvent is made on the basis of a number of factors including the choice of catalyst and whether it is desired to run the polymerization as a slurry or solution process. For most of the catalysts described in this invention, the preferred solvents are chlorinated hydrocarbons such as methylene chloride and 1,2-dichloroethane and aromatic hydrocarbons such as chlorobenzene and nitrobenzene, with simple hydrocarbons being less preferred due to the resulting lower conversion of the functional NB-type monomer(s). Surprisingly we have discovered that certain of the catalyst systems, most notably the multicomponent catalysts based on Group VIII metal compounds and alkylaluminum halides, specifically, monoalkylaluminum dihalides, (e.g., ethylaluminum dichloride), and the type 2 catalysts referred to above also give excellent results (and high monomer conversion) when run in simple hydrocarbons such as heptane, cyclohexane, and toluene.
The molar ratio of total monomer to Group VIII metal for the single and multicomponent catalysts can run from 20:1 to 100,000:1, preferably 50:1 to 20,000:1, and most preferably 100:1 to 10,000:1.
In the multicomponent catalyst systems, the cocatalyst metal (e.g., aluminum, zinc, magnesium, and lithium) to Group VIII metal molar ratio ranges from less than or equal to 100:1, preferably less than or equal to 30:1, and most preferably less than or equal to 20:1.
The third component is employed in a molar ratio to Group VIII metal ranging from 0.25:1 to 20:1. When acids are employed as third components, the acid to Group VIII metal range is less than or equal to 4:1, preferably less than or equal to 2:1.
The temperature at which the polymerization reactions of the present invention are carried out typically ranges from xe2x88x92100xc2x0 C. to 120xc2x0 C., preferably xe2x88x9260xc2x0 C. to 90xc2x0 C., and most preferably xe2x88x9210xc2x0 C. to 80xc2x0 C.
The optimum temperature for the present invention is dependent on a number of variables, primarily the choice of catalyst and the choice of reaction diluent. Thus, for any given polymerization the optimum temperature will be experimentally determined taking these variables into account.
In the course of developing these catalyst and polymer systems we have observed that the palladium-carbon bond which links the palladium catalysts to the growing polymer chain is particularly stable. This is a major benefit in polymerizing polycyclic monomers bearing acid labile groups, esters and carboxylic acid functionalities since the palladium catalysts are extremely tolerant to such functionalities. However, this stability also makes it very difficult to remove the palladium catalyst residues from the resulting polymer. During the development of these new compositions, we discovered that the palladium-carbon bond can be conveniently cleaved (resulting in precipitation of palladium metal which can be removed by filtration or centrifugation) using carbon monoxide, preferably in the presence of a protic solvent such as an alcohol, moisture, or a carboxylic acid.
The polymers obtained by the process of the present invention are produced in a molecular weight (Mn) range from about 1,000 to about 1,000,000, preferably from about 2,000 to about 700,000, and more preferably from about 5,000 to about 500,000 and most preferably from about 10,000 to about 50,000.
Molecular weight can be controlled by changing the catalyst to monomer ratio, i.e., by changing the initiator to monomer ratio. Lower molecular weight polymers and oligomers may also be formed in the range from about 500 to about 500,000 by carrying out the polymerization in the presence of a chain transfer agent. Macromonomers or oligomers comprising from 4 to 50 repeating units can be prepared in the presence of a CTA (Chain Transfer Agent) selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, wherein at least one of the adjacent carbon atoms has two hydrogen atoms attached thereto. The CTA is exclusive of styrenes (non-styrenes), vinyl ethers (non-vinyl ether) and conjugated dienes. By non-styrenic, non-vinyl ether is meant that compounds having the following structures are excluded from the chain transfer agents of this invention: 
wherein A is an aromatic substituent and R is hydrocarbyl.
The preferred CTA compounds of this invention are represented by the following formula: 
wherein Rxe2x80x2 and Rxe2x80x3 independently represent hydrogen, branched or unbranched (C1 to C40) alkyl, branched or unbranched (C2 to C40) alkenyl, and halogen.
Of the above chain transfer agents the xcex1-olefins having 2 to 10 carbon atoms are preferred, e.g., ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene, and 1,6-octadiene, or isobutylene. Other CTA""s include allyl halides such as allyl chlorides, allyl bromides, etc., allyl trifluoro-acetates, xcex2-pineres, xcex1-pineres.
While the optimum conditions for any given result should be experimentally determined by a skilled artisan taking into the account all of the above factors there are a number of general guidelines which can be conveniently utilized where appropriate. We have learned that, in general, xcex1-olefins (e.g., ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene) are the most effective chain transfer agents with 1,1-disubstituted olefins (e.g., isobutylene) being less efficient. In other words, all other things being equal, the concentration of isobutylene required to achieve a given molecular weight will be much higher than if ethylene were chosen. Styrenic olefins, conjugated dienes, and vinyl ethers are not effective as chain transfer agents due to their propensity to polymerize with the catalysts described herein.
The CTA can be employed in an amount ranging from about 0.10 mole % to over 50 mole % relative to the moles of total NB-type monomer. Preferably, the CTA is employed in the range of 0.10 to 10 mole %, and more preferably from 0.1 to 5.0 mole %. As discussed above, depending on catalyst type and sensitivities, CTA efficiencies and desired end group, the concentration of CTA can be in excess of 50 mole % (based on total NB-functional monomer present), e.g., 60 to 80 mole %. Higher concentrations of CTA (e.g., greater than 100 mole %) may be necessary to achieve the low molecular weight embodiments of this invention such as in oligomer and macromonomer applications. It is important and surprising to note that even such high concentrations the CTA""s (with the exception of isobutylene) do not copolymerize into the polymer backbone but rather insert as terminal end-groups on each polymer chain. Besides chain transfer, the process of the present invention affords a way by which a terminal xcex1-olefinic end group can be placed at the end of a polymer chain.
Polymers of the present invention that are prepared in the presence of the instant CTA""s have molecular weights (Mn) ranging from about 1,000 to about 500,000, preferably from about 2,000 to about 300,000, and most preferably from about 5,000 to about 200,000.
The photoresist compositions of the present invention comprise the disclosed polycyclic compositions, a solvent, and an photosensitive acid generator (photoinitiator). Optionally, a dissolution inhibitor can be added in an amount of up to about 20 weight % of the composition. A suitable dissolution inhibitor is t-butyl cholate (J. V. Crivello et al., Chemically Amplified Electron-Beam Photoresists, Chem. Mater., 1996, 8, 376-381).
Upon exposure to radiation, the radiation sensitive acid generator generates a strong acid. Suitable photoinitiators include triflates (e.g., triphenylsulfonium triflate), pyrogallol (e.g., trimesylate of pyrogallol); onium salts such as triarylsulfonium and diaryliodium hexafluoroantimonates, hexafluoroarsenates, trifluoromethanesulfonates; esters of hydroxyimides, xcex1,xcex1xe2x80x2-bis-sulfonyl-diazomethanes, sulfonate esters of nitro-substituted benzyl alcohols and napthoquinone-4-diazides. Other suitable photoacid initiators are disclosed in Reichmanis et al., Chem. Mater. 3, 395, (1991). Compositions containing triarylsulfonium or diaryliodonium salts are preferred because of their sensitivity to deep UV light (193 to 300 nm) and give very high resolution images. Most preferred are the unsubstituted and symmetrically or unsymmetrically substituted diaryliodium or triarylsulfonium salts. The photoacid initiator component comprises about 1 to 100 w/w % to polymer. The preferred concentration range is 5 to 50 w/w %.
The photoresist compositions of the present invention optionally contain a sensitizer capable of sensitizing the photoacid initiator to longer wave lengths ranging from mid UV to visible light. Depending on the intended application, such sensitizers include polycyclic aromatics such as pyrene and perlene. The sensitization of photoacid initiators is well-known and is described in U.S. Pat. Nos. 4,250,053; 4,371,605; and 4,491,628 which are all incorporated herein by reference. The invention is not limited to a specific class of sensitizer or photoacid initiator.
The present invention also relates to a process for generating a positive tone resist image on a substrate comprising the steps of: (a) coating a substrate with a film comprising the positive tone resist composition of the present invention; (b) imagewise exposing the film to radiation; and (c) developing the image.
The first step involves coating the substrate with a film comprising the positive tone resist composition dissolved in a suitable solvent. Suitable substrates are comprised of silicon, ceramics, polymer or the like. Suitable solvents include propylene glycol methyl ether acetate (PGMEA) cyclohexanone, butyrolactate, ethyl lactate, and the like. The film can be coated on the substrate using art known techniques such as spin or spray coating, or doctor blading. Preferably, before the film has been exposed to radiation, the film is heated to an elevated temperature of about 90xc2x0 C. to 150xc2x0 C. for a short period of time of about 1 min. In the second step of the process, the film is imagewise exposed to radiation suitably electron beam or electromagnetic preferably electromagnetic radiation such as ultraviolet or x-ray, preferably ultraviolet radiation suitably at a wave length of about 193 to 514 nm preferably about 193 nm to 248 nm. Suitable radiation sources include mercury, mercury/xenon, and xenon lamps, x-ray or e-beam. The radiation is absorbed by the radiation-sensitive acid generator to produce free acid in the exposed area. The free acid catalyzes the cleavage of the acid labile pendant group of the copolymer which converts the copolymer from dissolution inhibitor to dissolution enhancer thereby increasing the solubility of the exposed resist composition in an aqueous base. Surprisingly, the exposed resist composition is readily soluble in aqueous base. This solubility is surprising and unexpected in light of the complex nature of the cycloaliphatic backbone and the high molecular weight of the norbornene monomer units bearing the carboxylic acid functionality. Preferably, after the film has been exposed to radiation, the film is again heated to an elevated temperature of about 90xc2x0 C. to 150xc2x0 C. for a short period of time of about 1 minute.
The third step involves development of the positive tone image with a suitable solvent. Suitable solvents include aqueous base preferably an aqueous base without metal ions such as tetramethyl ammonium hydroxide or choline. The composition of the present invention provides positive images with high contrast and straight walls. Uniquely, the dissolution property of the composition of the present invention can be varied by simply varying the composition of the copolymer.
The present invention also relates to an integrated circuit assembly such as an integrated circuit chip, multichip module, or circuit board made by the process of the present invention. The integrated circuit assembly comprises a circuit formed on a substrate by the steps of: (a) coating a substrate with a film comprising the positive tone resist composition of the present invention; (b) imagewise exposing the film to radiation; (c) developing the image to expose the substrate; and (d) forming the circuit in the developed film on the substrate by art known techniques.
After the substrate has been exposed, circuit patterns can be formed in the exposed areas by coating the substrate with a conductive material such as conductive metals by art known techniques such as evaporation, sputtering, plating, chemical vapor deposition, or laser induced deposition. The surface of the film can be milled to remove any excess conductive material. Dielectric materials may also be deposited by similar means during the process of making circuits. Inorganic ions such as boron, phosphorous, or arsenic can be implanted in the substrate in the process for making p or n doped circuit transistors. Other means for forming circuits are well known to those skilled in the art.
The following examples are detailed descriptions of methods of preparation and use of certain compositions of the present invention. The detailed preparations fall within the scope of, and serve to exemplify, the more generally described methods of preparation set forth above. The examples are presented for illustrative purposes only, and are not intended as a restriction on the scope of the invention.
As discussed above, photoresists are used to create and replicate a pattern from a photomask to a substrate. The efficacy of this transfer is determined by the wave length of the imaging radiation, the sensitivity of the photoresist and the ability of the photoresist to withstand the etch conditions which pattern the substrate in the exposed regions. Photoresists are most often used in a consumable fashion, where the photoresist is etched in the non-exposed regions (for a positive tone photoresist) and the substrate is etched in the exposed regions. Because the photoresist is organic and the substrate is typically inorganic, the photoresist has an inherently higher etch rate in the reactive ion etch (RIE) process, which necessitates that the photoresist needs to be thicker than the substrate material. The lower the etch rate of the photoresist matter, the thinner the photoresist layer has to be. Consequently, higher resolution can be obtained. Therefore, the lower the RIE rate of the photoresist, the more attractive it is from a process point of view. The etch rate is primarily determined by the polymer backbone, as shown below for the chlorine plasma etch process which is a RIE technique typically employed in semiconductor processing.
As used in the examples and throughout the specification the ratio of monomer to catalyst is based on a mole to mole basis.
Polymers 1 and 2 are primarily aromatic, whereas polymer 3 was copolymerized with a small amount of acrylate which increased its etch rate. Polymer 4 is completely based on acrylates to allow transparency at 193 nm (aromatic rings render the material opaque in this region, hence there are no viable resist candidates at 193 nm based on the traditional novolacs or p-hydroxystyrene). The etch rate almost doubled for this polymer. Polymer 5 had an etch rate even lower than the standard photoresist materials (1 and 2) in addition to providing transparency at 193 nm. Therefore, the backbone of polymer 5 (an addition cyclic olefin) prepared by a nickel multicomponent catalyst of this invention is an improvement over all previous attempts in the literature to provide a resist which functions at 193 nm with RIE characteristics comparable to commercial materials exposed at longer wave lengths. In fact, the addition cyclic olefin polymer may offer advantages in terms of etch resistance at longer wave lengths as well. It is in the literature (H. Gokan, S. Esho, and Y. Ohnishi, J. Electrochem. Soc. 130(1), 143 (1983)) that higher C/H ratios decreases the etch rate of polymeric materials. Based on this assumption, the etch rate of polymer 5 should be between the aromatic based systems and the acrylate systems. It is surprising that the addition cyclic olefin exhibits etch resistance superior to even the aromatic systems.
Catalyst A. Synthesis of (PhC(O)CH2PPh2)Ni(C6F5)2 
[(PhC(O)CHPPh2)Ni(Ph)]2 (0.150 g, 0.171 mol) was weighed into a 100 ml Kjeldahl flask in the dry box. Also in the dry box, 0.194 g of B(C6F5)3.3H2O (0.342 mol) was weighed into a separate flask. After each solid was dissolved separately in a minimum of toluene (about 15 ml each), the solution of B(C6F5)3.3H2O was added to the solution/slurry of the nickel dimer (it was not completely soluble in toluene). The mixture changed from a cloudy orange to a translucent red-brown color upon addition of the boron reagent. The solution was stirred for approximately one hour, after which time the toluene was removed in vacuo. The yellowish-brown solid was redissolved in a small amount of toluene and cooled to xe2x88x9220xc2x0 C. A yellow solid formed which was filtered and dried in vacuo. Yield 0.108 g (45% yield). 1H NMR (CD2Cl2): 7.90 (d, 2H), 7.67 (t, 3H), 7.48 (m, 4H), 7.20 (m, 6H), 4.19 (d, JPH=5 Hz, 2H). 31P{1H} NMR (C6D6): 26.8 (s). 19F NMR (C6D6): xe2x88x92115.8 (m, 2F), xe2x88x92119.0 (m, 2F), xe2x88x92159.8 (t, 1F), xe2x88x92160.9 (t, 1F), xe2x88x92162.9 (apparent t of d, 2F), xe2x88x92163.7 (apparent t, 2F). FD-MS: m/e 696 [M+] exhibits expected isotope pattern for nickel, exact mass 696.021080, calculated 696.021083. CI-MS: m/e 529 [M+xe2x80x94C6F5] exhibits expected isotope pattern for nickel, exact mass 529.029065, calculated mass 529.029067.
Catalyst A. Alternative synthesis of (PhC(O)CH2PPh2)Ni(C6F5)2 
PhC(O)CH2PPh2 was prepared as described in Inorg. Chem. 1986, 25, 3765. (6-toluene)Ni(C6F5)2 (0.10 g, 0.21 mmol) was dissolved in 10 ml of toluene. To this solution PPh2CH2C(O)Ph (0.063 g, 0.21 mmol) in 10 ml of toluene was added dropwise. The color of the solution turned yellow-brown after 10 min., and a yellow powder began to precipitate from solution. After stirring at room temperature for 1 hour, the solvent was removed in vacuo resulting in a yellow solid. This was dissolved in 10 ml of CH2Cl2, filtered and stored at xe2x88x9220xc2x0 C. Bright yellow crystals were obtained in quantitative yield after 2 days. The x-ray crystal structure of (PhC(O)CH2PPh2)Ni(C6F5)2 is shown in FIG. 1.
Catalyst B. Synthesis of cis-Ni(THF)2(C6F5)2 
Pentafluorophenylbromide (12.9 g) was added slowly (1 ml every 20 min.) via an addition funnel to a flask containing of magnesium turnings in 50 ml of THF equipped with a stir bar and a condenser. During the addition of the bromide, the THF solution turned dark and began to reflux. After about 2 hours, the resulting brown solution was added to a flask containing NiBr2 (5.03 g) in 25 ml of THF. The resulting mixture was then refluxed for 2 hours to give a red solution. The solution was allowed to cool and 35 ml of 1,4-dioxane was added. The solution became orange and insoluble material appeared. The mixture was stored at 5xc2x0 C. overnight. The next day, the solution was allowed to warm to room temperature and then filtered to remove insoluble material. The insoluble material was washed with 1.4-dioxane to give a grey material. The red-orange filtrate was placed stored at xe2x88x9220xc2x0 C. overnight. The next day 3.0 g (23% yield) of orange crystalline cis-Ni(THF)2(C6F5)2 were collected. The x-ray crystal structure of cis-Ni(THF)2(C6F5)2 is shown in FIG. 2.
Catalyst B. Alternative synthesis of cis-Ni(THF)2(C6F5)2 
To a cold (xe2x88x9278xc2x0 C.) slurry of Ni(COD)2 (10.0 g) in a mixture of THF (30 ml) and diethylether (40 ml) was added a solution of C6F5C(O)Cl (8.4 g) in 25 ml of diethylether dropwise. No color change was evident after addition. The mixture was warmed to 0xc2x0 C. for 1 hour. During this time the color of the solution changed to orange and an orange precipitate formed. After warming to room temperature all of the yellow nickel starting material was consumed to yield an orange solution and solid. The slurry was concentrated in vacuo (to ca. 20 ml) and cyclohexane was added (120 ml) to precipitate out any remaining soluble material. The solvents were decanted and washed with cyclohexane (2xc3x9725 ml). The solid was dried in vacuo.
The orange solid was extracted twice with 50 ml of toluene. During the extractions, the initial light orange solution became red-orange. The extractions were combined and cooled to xe2x88x9220xc2x0 C. to yield orange crystals. The mother liquor was stripped of solvent and extracted once again with toluene (2xc3x9750 ml), combined and cooled to xe2x88x9220xc2x0 C. After a few days, this solution yielded a second batch of orange crystals. The combined yields were 13%. The crystals decomposed at 183xc2x0 C. and were pure by NMR spectroscopy.
Catalyst C. Synthesis of (toluene)Ni(C6F5)2 
This procedure followed a previously published method found in Organometallics 1985, 4, 571. Magnesium turnings (0.945 g) was weighed in a three neck 250 ml flask equipped with gas inlet, stir bar, and addition funnel (a reflux condenser is also recommended). After purging with argon, 10 ml of dry diethylether was added. With stirring, bromopentafluorobenzene (1 ml) was added dropwise at room temperature. Ten minutes after the addition of bromopentafluorobenzene, a light brown color appeared in the ethereal solution. At this point, a solution of bromopentafluorobenzene (3.38 ml) in 15 ml of ether was added dropwise at a rate which maintained reflux of the ether. The brown color became very dark. The mixture was stirred for 1 hour at room temperature.
In the dry box, anhydrous nickel bromide (3.83 g) was weighed into a 200 ml Kjeldahl flask equipped with a stir bar. Only finely divided nickel bromide powder was used. Also in the dry box silver trifluoroacetate (7.78 g) was weighed into a solid addition tube which was subsequently attached to the Kjeldahl. About 75 ml of diethylether was added to the nickel bromide to give an orange slurry. To this slurry was added the solid silver salt which gave a slightly exothermic reaction and a green solution of the soluble nickel salt. The reaction mixture was allowed to continue to stir for three hours. The orange color of the insolubles changed to a dull yellow-orange as silver bromide replaced the nickel bromide. The mixture was filtered to yield a green solution that was used in the step below.
The Grignard solution was cooled to 0xc2x0 C. and the nickel trifluoroacetate solution was added dropwise over 30 min. The solution was stirred for one hour at 0xc2x0 C. and then allowed to warm to room temperature. Then 40 ml of toluene was added to the solution. The resulting dark brown solution was evaporated to dryness. To the resulting dark brown solid was added 100 ml of toluene and the brown solution with a grey solid was stirred overnight. The slurry was concentrated to about 25 ml with heating to 45-50xc2x0 C. The grey solid was filtered and washed with toluene (2xc3x9720 ml). The solutions were combined and dried overnight in vacuo. The resulting light brown solid was extracted with 50 ml of toluene and filtered. The insoluble grey solid was washed with 5 ml of toluene and the solutions were combined. Slow evaporation of the dark brown solution to ca. 5 ml gave a crystalline material. The remaining solvent was evaporated and the crystals were washed with heptane and filtered and dried in vacuo to give 4.59 g (54%) of brick red crystals.
Catalyst A
Synthesis of (PhC(O)CH2PPh2)Ni(C6F5)2 
[(PhC(O)CHPPh2)Ni(Ph)]2 (0.150 g, 0.171 mol) was weighed into a 100 ml Kjeldahl flask in the dry box. Also in the dry box, 0.194 g of B(C6F5)3.3H2O (0.342 mol) was weighed into a separate flask. After each solid was dissolved separately in a minimum of toluene (about 15 ml each), the solution of B(C6F5)3.3H2O was added to the solution/slurry of the nickel dimer (it was not completely soluble in toluene). The mixture changed from a cloudy orange to a translucent red-brown color upon addition of the boron reagent. The solution was stirred for approximately 1 hour, after which time the toluene was removed in vacuo. The yellowish-brown solid was redissolved in a small amount of toluene and cooled to xe2x88x9220xc2x0 C. A yellow solid formed which was filtered and dried in vacuo. Yield 0.108 g (45% yield). 1H NMR (CD2Cl2): 7.90 (d, 2H), 7.67 (t, 3H), 7.48 (m, 4H), 7.20 (m, 6H), 4.19 (d, JPH=5 Hz, 2H). 31 P{1H} NMR (C6D6): 26.8 (s). 19F NMR (C6D6): xe2x88x92115.8 (m, 2F), xe2x88x92119.0 (m, 2F), xe2x88x92159.8 (t, 1F), xe2x88x92160.9 (t, 1F), xe2x88x92162.9 (apparent t of d, 2F), xe2x88x92163.7 (apparent t, 2F). FD-MS: m/e 696 [M+] exhibits expected isotope pattern for nickel, exact mass 696.021080, calculated 696.021083. CI-MS: m/e 529 [M+xe2x80x94C6F5] exhibits expected isotope pattern for nickel, exact mass 529.029065, calculated mass 529.029067.
Catalyst A
Alternative Synthesis of (PhC(O)CH2PPh2)Ni(C6F5)2 
PhC(O)CH2PPh2 was prepared as described in Inorg. Chem. 1986, 25, 3765. (xcex76-toluene)Ni(C6F5)2 (0.10 g, 0.21 mmol) was dissolved in 10 ml of toluene. To this solution PPh2CH2C(O)Ph (0.063 g, 0.21 mmol) in 10 ml of toluene was added dropwise. The color of the solution turned yellow-brown after 10 min., and a yellow powder began to precipitate from solution. After stirring at room temperature for 1 hour, the solvent was removed in vacuo resulting in a yellow solid. This was dissolved in 10 ml of CH2Cl2, filtered and stored at xe2x88x9220xc2x0 C. Bright yellow crystals were obtained in quantitative yield after 2 days. The x-ray crystal structure of (PhC(O)CH2PPh2)Ni(C6F5)2 is shown in FIG. 1.
Catalyst B
Synthesis of cis-Ni(THF)2(C6F5)2 
Pentafluorophenylbromide (12.9 g) was added slowly (1 ml every 20 min.) via an addition funnel to a flask containing magnesium turnings in 50 ml of THF equipped with a stir bar and a condenser. During the addition of the bromide, the THF solution turned dark and began to reflux. After about 2 hours, the resulting brown solution was added to a flask containing NiBr2 (5.03 g) in 25 ml of THF. The resulting mixture was then refluxed for 2 hours to give a red solution. The solution was allowed to cool and 35 ml of 1,4-dioxane was added. The solution became orange and insoluble material appeared. The mixture was stored at 5xc2x0 C. overnight. The next day, the solution was allowed to warm to room temperature and then filtered to remove insoluble material. The insoluble material was washed with 1.4-dioxane to give a grey material. The red-orange filtrate was placed stored at xe2x88x9220xc2x0 C. overnight. The next day 3.0 g (23% yield) of orange crystalline cis-Ni(THF)2(C6F5)2 were collected. The x-ray crystal structure of cis-Ni(THF)2(C6F5)2 is shown in FIG. 2.
Catalyst B
Alternative Synthesis of cis-Ni(THF)2(C6F5)2 
To a cold (xe2x88x9278xc2x0 C.) slurry of Ni(COD)2 (10.0 g) in a mixture of THF (30 ml) and diethylether (40 ml) was added a solution of C6F5C(O)Cl (8.4 g) in 25 ml of diethylether dropwise. No color change was evident after addition. The mixture was warmed to 0xc2x0 C. for 1 hour. During this time the color of the solution changed to orange and an orange precipitate formed. After warming to room temperature all of the yellow nickel starting material was consumed to yield an orange solution and solid. The slurry was concentrated in vacuo (to ca. 20 ml) and cyclohexane was added (120 ml) to precipitate out any remaining soluble material. The solvents were decanted and washed with cyclohexane (2xc3x9725 ml). The solid was dried in vacuo.
The orange solid was extracted twice with 50 ml of toluene. During the extractions, the initial light orange solution became red-orange. The extractions were combined and cooled to xe2x88x9220xc2x0 C. to yield orange crystals. The mother liquor was stripped of solvent and extracted once again with toluene (2xc3x9750 ml), combined and cooled to xe2x88x9220xc2x0 C. After a few days, this solution yielded a second batch of orange crystals. The combined yields were 13%. The crystals decomposed at 183xc2x0 C. and were pure by NMR spectroscopy.
Catalyst C
Synthesis of (toluene)Ni(C6F5)2 
This procedure followed a previously published method found in Organometallics 1985, 4, 571. Magnesium turnings (0.945 g) was weighed in a three neck 250 ml flask equipped with gas inlet, stir bar, and addition funnel (a reflux condenser is also recommended). After purging with argon, 10 ml of dry diethylether was added. With stirring, bromopentafluorobenzene (1 ml) was added dropwise at room temperature. Ten minutes after the addition of bromopentafluorobenzene, a light brown color appeared in the ethereal solution. At this point, a solution of bromopentafluorobenzene (3.38 ml) in 15 ml of ether was added dropwise at a rate which maintained reflux of the ether. The brown color became very dark. The mixture was stirred for 1 hour at room temperature.
In the dry box, anhydrous nickel bromide (3.83 g) was weighed into a 200 ml Kjeldahl flask equipped with a stir bar. Only finely divided nickel bromide powder was used. Also in the dry box silver trifluoroacetate (7.78 g) was weighed into a solid addition tube which was subsequently attached to the Kjeldahl. About 75 ml of diethylether was added to the nickel bromide to give an orange slurry. To this slurry was added the solid silver salt which gave a slightly exothermic reaction and a green solution of the soluble nickel salt. The reaction mixture was allowed to continue to stir for three hours. The orange color of the insolubles changed to a dull yellow-orange as silver bromide replaced the nickel bromide. The mixture was filtered to yield a green solution of nickel trifluoroacetate (II) that was used in the step below.
The Grignard solution was cooled to 0xc2x0 C. and the green nickel trifluoroacetate solution was added dropwise over 30 min. The solution was stirred for one hour at 0xc2x0 C. and then allowed to warm to room temperature. Then 40 ml of toluene was added to the solution. The resulting dark brown solution was evaporated to dryness. To the resulting dark brown solid was added 100 ml of toluene and the brown solution with a grey solid was stirred overnight. The slurry was concentrated to about 25 ml with heating to 45-50xc2x0 C. The grey solid was filtered and washed with toluene (2xc3x9720 ml). The solutions were combined and the solvent was removed overnight in vacuo. The resulting light brown solid was extracted with 50 ml of toluene and filtered. The insoluble grey solid was washed with 5 ml of toluene and the solutions were combined. Slow evaporation of the dark brown solution to ca. 5 ml gave a crystalline material. The remaining solvent was evaporated and the crystals were washed with heptane and filtered and dried in vacuo to give 4.59 g (54%) of brick red crystals.
Catalyst D
Synthesis of (Ph2NC(O)CH2PPh2)Ni(C6F5)2 
Ph2NC(O)CH2PPh2 was prepared as described in J. Chem. Res. (S), 1993, 380. (xcex76-toluene)Ni(C6F5)2 (0.10 g, 0.21 mmol) was dissolved in 5 ml of toluene. To this solution Ph2NC(O)CH2PPh2 (0.081 g, 0.21 mmol) in 5 ml of toluene was added dropwise. The color of the solution turned light yellow-brown. After stirring at room temperature for 1 hour, the solvent was removed in vacuo resulting in a light yellow powder.
Catalyst E
Synthesis of (PhC(O)CH2CH2PPh2)Ni(C6F5)2 
(PhC(O)CH2CH2PPh2) was prepared as described in J. Pract. Chem. 1972, 315. (xcex76-toluene)Ni(C6F5)2 (0.50 g, 1.0 mmol) was dissolved in 20 ml of toluene. To this solution PPh2CH2C(O)Ph (0.33 g, 1.0 mmol) in 10 ml of toluene was added dropwise. The color of the solution turned yellow after 10 m. After 1 hour, the solvent was removed in vacuo to yield a solid.
Catalyst F
Ni(COD)2 (0.60 g) was dissolved in 30 ml of THF. A solution of pentafluorobenzoyl chloride (0.315 ml in 3 ml of THF) was added to the above solution. An immediate color change from yellow to orange occurred. The solution was stirred for 30 min. at room temperature after which the volume of the solution was reduced in vacuo to about 3 ml. To this solution was added cyclohexane to precipitate a pink solid. The solvent was decanted and the product was dried in vacuo for 1 hour. Yield 0.80 g.
Catalyst G
Ni(COD)2 (3.0 g) was dissolved in 100 ml of toluene. To this solution was added a solution of pentafluorobenzoic acid (2.33 g in 30 ml of toluene) was added to the above solution. An immediate color change from yellow to red/brown occurred. The solution was stirred for 1 hour at room temperature after which time the toluene was removed in vacuo. The resulting brown solid was dissolved in hot cyclohexane and allowed to cool resulting in a brown powder. The solvent was decanted and the powder was dried in vacuo. Yield 2.8 g.
Catalyst H
Ni(THF)2(C6F5)2 (0.126 g) was dissolved in about 10 ml of toluene. To this solution was added 0.050 ml of beta-pinene in 2 ml of toluene. The orange color of the starting material changed immediately to blue. The solution was stirred for two hours at room temperature after which time the solvent was removed in vacuo to give a blue, grey solid.
Catalyst I
Ni(COD)2 (0.130 g) was dissolved in 10 ml of THF and cooled to xe2x88x9278xc2x0 C. To this solution was added a solution of 2,4,6-trifluorobenzoyl chloride (0.092 g) in 4 ml of THF. The solution was allowed to warm to room temperature after which time the solution darkened to a dark orange color. The solution was concentrated to about 2 ml in vacuo and cyclohexane was added (35 ml) to precipitate out a brown solid. The solvent was decanted and the solid was dried in vacuo.
Catalyst J
Synthesis of Ni(PPh3)2(C6F5)2 
To a small Schlenk flask, in the dry box, was added (toluene)Ni(C6F5)2 (0.33 g) and PPH3 (0.36 g) followed by toluene (20 ml). The solution was stirred for 20 minutes. The solvent was then removed in vacuo to yield the complex.
Catalyst K
Synthesis of tris(orthotolylphosphine)Ni(C6F5)2. To a small Schlenk flask, in an inert atmosphere box, was added tris(orthotolyl)phosphine (0.52 g, 1.7 mmol) and (toluene)Ni(C6F5)2 (0.417 g, 0.85 mmol) followed by toluene (15 ml) which resulted in the formation of a blood red solution. The solvent was removed to afford the phosphine adduct as a red solid.
Catalyst L
Synthesis of (1,2-dimethoxyethane)Ni(2,4,6-tris(trifluoro methyl)phenyl)2 
Preparation of lithium(2,4,6-tris(trifluoromethyl)phenyl). To a clean, dry Kjeldahl flask was added 2,4,6-tris(trifluoromethyl)benzene (1.65 ml, 8.86 mmol) dissolved in a mixture of diethylether (20 ml) and hexane (20 ml). To this solution, cooled to 15xc2x0 C. under argon, was added n-butyllithium (3.54 ml of a 2.5 molar solution in hexanes, 8.86 mmol). The solution turned yellow immediately. The solution was allowed to warm to ambient temperature and then allowed to stir at this temperature for an additional 60 minutes.
Preparation of (1,2-dimethoxyethane)Ni(2,4,6-tris(trifluoromethyl)phenyl)2. The above solution was transferred (under argon) to a second Kjeldahl flask containing (1,2-dimethoxyethane)NiCl2 (0.973 g, 4.43 mmol) in a mixture of diethylether (20 ml) and hexane (20 ml). The mixture turned red-brown in color within 10 minutes and was allowed to stir at ambient temperature for 48 hours. The solvent was then removed and the solid residue was extracted with toluene (50 ml) and filtered through Celite. The toluene was removed to afford a slightly oily brown residue which was washed with hexane (3 aliquots of 20 ml) to afford the product, a new compound, (1,2-dimethoxyethane)Ni(2,4,6-tris(trifluoromethyl)phenyl)2, as a purple microcrystalline solid. The new compound was characterized fully using NMR and MS techniques. Characteristic of the new compound is a singlet in the 19F NMR at xe2x88x9262.6 ppm in deuterobenzene and in the mass spectrum the molecular ion (with essentially no fragmentation) at 710. The x-ray crystal structure of this compound is shown in FIG. 3.
Catalyst M
Synthesis of (Et4N)2[Ni(C6F5)2Cl2]2 
The procedure employed was similar to that demonstrated by K. Klabunde et al, Inorganic Chemistry, 1989, Volume 28, pages 2414-2419. Tetraethylammonium chloride (Et4NCl) was recrystallized from isopropanol/toluene (1:2) and dried by under vacuum prior to use. At room temperature, a dichloromethane solution of Et4NCl (0.085 g, 0.516 mmol) was added to (xcex76-toluene)Ni(C6F5)2 (0.25 g, 0.516 mmol) dissolved quickly in dichloromethane (5 ml). The red brown solution turned a deeper, brighter red almost immediately after addition of the Et4NCl. The solution was stirred for a four hours and then filtered. The solution was then layered with toluene (10 ml). The dark red crystals of (Et4N)2[Ni(C6F5)2Cl2]2 were collected by filtration. Yield=0.255 g, 83%). The compound was characterized analyzed by 1H and 19F NMR.
Catalyst M
Alternative Synthesis of (Et4N)2[Ni(C6F5)2Cl2]2 
At 0xc2x0 C., Zn(C6F5)2(dme) (1.0 g) dissolved in dichloromethane was added to a sample of light blue, (Et4N)2NiCl4 (0.942 g) stirring in dichloromethane (15 ml). The light blue suspension slowly reacted to yield an orange red murky solution. The product was stripped to dryness and then redissolved in tetrahydrofuran (THF), filtered to remove the ZnCl2, and reprecipitated with pentane. The (Et4N)2[Ni(C6F5)2Cl2]2 product was collected by filtration and washed with pentane to yield an orange red solid. Recrystallization of this product to a achieve red crystals can be achieved from either dichloromethane/toluene or THF/pentane mixtures. Yield=1.07 g (97%).
Catalyst N
Synthesis of (xcex73-CH3C(CH)2)Ni(PPh3)(C6F5).
(xcex73-CH3C(CH)2)Ni(PPh3)Cl was prepared by adding of one equivalent of triphenylphosphine (0.78 g in toluene (10 ml) to [(xcex73-CH3C(CH)2)NiCl]2 (0.5 g) dissolved in toluene (20 ml). After 16 hours of reaction at room temperature an orange brown powder (0.85 g, 83%) was filtered from the reaction. Recrystallization from toluene and pentane at xe2x88x9230xc2x0 C. yielded orange crystals. The product was characterized by 1H and 31P NMR spectroscopies.
A quantity of Zn(C6F5)2(dme) (0.030 g) was dissolved in diethyl ether (10 ml) and cooled to xe2x88x9278xc2x0 C. This reagent was added dropwise into a diethyl ether solution of (xcex73-CH3C(CH)2)Ni(PPh3)Cl (0.05 g) held at xe2x88x9278xc2x0 C. After about 10 minutes the solution colored changed from its original orange to yellow. After 18 hours at room temperature, the solvent was removed leaving a crystalline red-yellow solid. The product was recrystallized from toluene and pentane to give (xcex73-CH3C(CH)2)Ni(PPh3)(C6F5). The product was characterized as being
Catalyst O
Synthesis of (xcex73-CH3C(CH)2)Ni(PCy3)(C6F5)
(xcex73-CH3C(CH)2)Ni(PCy3)Cl was prepared by adding of one equivalent of tricyclohexylphosphine (PCy3) (1.0 g in diethyl ether) to [(xcex73-CH3C(CH)2)NiCl]2 (0.532 g) dissolved in diethyl ether (15 ml). After 48 hours of reaction at room temperature an dark yellow solution was obtained. The solids were filtered from the reaction and the yellow solution evaporated to yield a dark yellow powder (1.1 g, 87%). Recrystallization from diethyl ether/pentane at xe2x88x9230xc2x0 C. yielded yellow-orange crystals. The product was characterized by 1H and 31 P NMR spectroscopies.
A quantity of Zn(C6F5)2(dme) (0.028 g) was dissolved in diethyl ether (15 ml) and cooled to xe2x88x9278xc2x0 C. This reagent was added dropwise into a diethyl ether solution of (xcex73-CH3C(CH)2)Ni(PCy3)Cl (0.05 g) held at xe2x88x9278xc2x0 C. After about 15 minutes the solution colored changed from its original dark orange to yellow. After 18 hours at room temperature, the solvent was removed leaving a crystalline yellow solid. The product was recrystallized from toluene and pentane to give (xcex73-CH3C(CH)2)Ni(PCy3)(C6F5). The product was characterized as being pure by 1H and 31P NMR spectroscopies.
Catalyst P
Synthesis of Ni(2,4,6-tris(trifluoromethyl)phenyl)2 
Preparation of lithium(2,4,6-tris(trifluoromethyl)phenyl). To a clean, dry Kjeldahl flask was added 2,4,6-tris(trifluoromethyl)benzene (5.0 g, 17.72 mmol) dissolved in diethylether (20 ml) and hexane (20 ml). To this solution, cooled to 15xc2x0 C. under argon, was added n-butyllithium (3.54 ml of a 2.5 molar solution in hexanes, 8.86 mmol). The solution turned yellow immediately. The solution was allowed to warm to ambient temperature and then allowed to stir at this temperature for an additional 60 minutes.
Preparation of Ni(2,4,6-tris(trifluoromethyl)phenyl)2. The above solution was transferred (under argon) to a second Kjeldahl flask containing anhydrous NiCl2 (1.16 g, 9.0 mmol) in a mixture of diethylether (20 ml) and hexane (20 ml). The mixture was allowed to stir at ambient temperature for 96 hours. The solvent was then removed and the solid residue was extracted with toluene (50 ml) and filtered through Celite. The toluene was removed to afford a slightly oily brown residue which was then extracted again with hexane (3 aliquots of 20 ml) to afford the product Ni(2,4,6-tris(trifluoromethyl)phenyl)2 as a brown solid. The compound was characterized fully using NMR techniques.
Catalyst Component Q
Synthesis of Ni(PhC(O)CHPPh2)(Ph)(PPh3). This preparation followed a published report in J. Polym. Sci. 1987, 25, 1989. A toluene slurry (150 ml) of PPh3 (5.00 g, 19.1 mmol) and the ylid PhC(O)CHPPh3 (7.30 g, 19.1 mmol) was added to a chilled (0xc2x0 C.) toluene slurry (80 ml) of Ni(COD)2 (5.30 g, 19.1 mmol). Upon completion of the addition, the mixture became a red-brown slurry. The mixture was allowed to warm to room temperature and stirred for 21 hours. The mixture was then heated to 50xc2x0 C. for 2 hours. The mixture was cooled to room temperature and allowed to stir for an additional 16 hours. The mixture was filtered to give a red-brown filtrate which upon removal of solvent in vacuo gave a brown residue. The residue was dissolved in toluene (50 ml) from which a tan precipitate formed upon addition of 50 mL of hexane. The mixture was stored in the freezer overnight to give a gold-tan solid which was filtered, washed with hexane, and dried. Yield 10.5 g (79%).
Catalyst Component R
Synthesis of Ni(OC(O)(C6H4)PPh2)(H)(PCy3). Ni(COD)2 (2.00 g, 7.27 mmol) was dissolved in 100 mL of toluene and cooled to xe2x88x9230xc2x0 C. To this solution was added a toluene solution (50 ml) of 2-diphenylphosphino)benzoic acid (2.22 g, 7.27 mmol). The mixture was stirred at xe2x88x9230xc2x0 C. for 30 min. and then warmed to xe2x88x9210xc2x0 C. and stirred for 1 hour. To this mixture was added triphenylphosphine (2.03 g, 7.27 mmol) in 50 ml of toluene. The mixture was stirred at room temperature for one hour. The solvent was removed in vacuo to give a light yellow-brown solid. Yield of crude product was 2.87 g (61%).
Catalyst Component S
Synthesis of Ni(PhC(O)CHPPh2)(Ph)(pyridine). This compound was synthesized using a procedure published previously in J. Polym. Sci 1987, 25, 1989.
Catalyst Component T
Synthesis of Ni(PhC(O)CHPPh2)(Ph)(CH2xe2x95x90PPh3). This compound was synthesized using a procedure published previously in Angew. Chem., Int. Ed. Engl. 1985, 24, 599.
Catalyst Component U
Synthesis of [Ni(PhC(O)CHPPh2)(Ph)]2. This compound was synthesized by reacting Ni(PhC(O)CHPPh2)(Ph)(PPh3) (0.76 g) with Rh(acetylacetonate)(C2H4)2 (0.14 g) in a minimum amount of toluene (about 25 ml). After stirring the mixture for 4 hours, the precipitated solid was filtered and dried overnight in vacuo to yield 0.48 g of a yellow-brown solid.
Catalyst Component V
(bpy)Ni(NBD)2. Dipyridyl (1.09 g) and bis(1,5-cyclooctadiene) nickel (1.93 g) were dissolved in diethyl ether. The dipyridyl solution was added to the nickel solution with stirring. Immediately a violet color developed. The solution was allowed to react for approximately 5 hours. The solution was cooled to xe2x88x9278xc2x0 C. and a diethyl ether solution of norbornadiene (2.88 ml) was added slowly. The mixture was allowed to warm to room temperature. No color change was noted after 1.5 hours. An additional 2.88 ml of norbornadiene in diethyl ether was added. The mixture was allowed to stir at room temperature overnight after which time a dark green precipitate resulted which was isolated by filtration, washed with cold ether and heptane, and dried in vacuo to a yield black solid. Yield 2.35 g (84%).
Catalyst Component W
Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel (II), or Ni(dpm)2. This preparation follows a published procedure in Inorg. Chem. 1973, 12, 2983. A solution of 2,2,6,6-tetramethyl-3,5-heptanedione (5.00 g) in 13.5 mL of ethanol was prepared. A solution of 3.93 g of nickel(II) nitrate hexahydrate in 35 ml of a 50% ethanol/water mixture was added to the above solution. With stirring, a solution (50% ethanol/water) of 1.08 g of NaOH was added with immediate precipitation of a green solid. The mixture was diluted with 200 mL of a 50% ethanol/water mixture, filtered, and washed with more ethanol/water mixture. The resulting green solid was air dried overnight in oven at 110xc2x0 C. to a constant weight. The green solid changed to a purple color. The solid was then recrystallized from 1,2-dichloroethane, filtered and dried. Yield 1.91 g of a purple solid.
Catalyst Component X
Synthesis of (toluene)Ni(SiCl3)2. (Toluene)Ni(SiCl3)2 was prepared following the method of Klabunde et al., Organometallics, 1985, 3, 571.
Catalyst Component Y
Synthesis of [(CH3)(C12H25)3N]2[NiCl4]
[(CH3)(C12H25)3N]2[NiCl4] was prepared by reacting NiCl2.6H2O with 2 equivalents of tridodecylmethylammonium chloride in absolute ethanol and removing the solvent. A light blue oil was obtained in 100% yield.
Catalyst Component Z
Synthesis of (Et4N)2[NiCl4]
(Et4N)2[NiCl4] was prepared by reacting NiCl2(dme) with 2 equivalents of tetraethylammonium chloride in anhydrous dimethoxyethane and removing the solvent. A light blue powder was obtained in 100% yield.
Arylating Agent B(C6F5)3.3H2O
The synthesis of reported here is based on a prior publication (see U.S. Pat. 5,296,433, 1994). A 3.15 wt % solution of B(C6F5)3 in Isopar(copyright)E (50 ml, 2.22 mmol) was placed in a 200 ml Kjeldahl flask equipped with a magnetic stir bar. Approximately 50 ml of cyclohexane was added to this solution followed by 3 equiv of deoxygenated, demineralized water (0.120 ml, 6.67 mmol). Which resulted in precipitation of a white, microcrystalline solid. The slurry was stirred for 30 m, the solvent was decanted, and the resulting solid was dried in vacuo. Yield, 0.826 g (66%). 19F NMR (C6D6): xe2x88x92134.7 (apparent d, 2F), xe2x88x92154.7 (apparent t, 1F), xe2x88x92162.6 (apparent t, 2F). FI-MS: m/z 512 [M+], evidently loss of water occurred in mass spectrometer. IR (Nujol): 3666 m, 3597 m, 3499 m, 2950 sh, 2920 s, 1647 m, 1602 m, 1520 s, 1468 s, 1379 m, 1288 m, 1111 m, 1098 m, 969 s, 859 w, 797 w, 771 w, 676 w, 614 w.
Arylating Agent Zn(C6F,5)2.DME
This synthesis method is a modification of the procedures outlined by D. Naumann and H. Lange, Journal of Fluorine Chemistry, Volume 26, 1984, pages 435-444. Iodopentafluorobenzene, C6F5I, (5.88 g, 20 mmoles) and dimethoxyethane (0.9012 g, 10 mmoles) were mixed together in a glass vial and cooled to xe2x88x9230xc2x0 C. To this solution was added a quantity of diethylzinc (1.235 g, 10 mmoles) that had also been cooled to xe2x88x9230xc2x0 C. The reaction mixed was slowly warmed to room temperature. The reaction vessel was scraped with the tip of a glass pipette and crystallization immediately occurred. The white powder was washed 3 times with pentane to remove the ethyl iodide reaction product and the Zn(C6F5)2(dme) dried to a white microcrystaline powder. Yield=72%. The Zn(C6F5)2(dme) sample was analyzed by 1H and 19F NMR spectroscopies and found to be pure. The thermal stability of Zn(C6F5)2(dme) was determined by performing a differential scanning calorimetric measurement at a temperature ramping rate of 20xc2x0 C./min. This method provided a sharp melting point at 108xc2x0 C. and indicated no decomposition below 300xc2x0 C.
Arylating Agent Zn(2,4,6-tris(trifluoromethyl)phenyl)2 
Zn(2,4,6-tris(trifluoromethyl)phenyl)2 was prepared by a variation of the orginal literature synthesis given by F. Edelmann et al., Organometallics, Volume 11, 1992, pages 192-5. ZnCl2 was added to a freshly prepared sample of 2,4,6-tris(trifluoromethyl)phenyllithium in diethyl ether. After refluxing for 6 hours the solvent was removed and the solids extracted with toluene. After removal of the lithium chloride the solvent is removed to yield an off-white solid. In our hands, the vacuum distillation of the crude was deemed unnecessary and the white crystalline product was recrystallized from pentane at xe2x88x9235xc2x0 C. Yield=53%. The product of Zn(2,4,6-tris(trifluoromethyl)phenyl)2 was characterized by 1H and 19F NMR spectroscopies.